Separator for Electricity Storage Device, Laminate and Porous Film

ABSTRACT

An object is to provide a separator excellent in adhesiveness to electrodes and a separator for an electricity storage device also excellent in handling performance. A separator for an electricity storage device having a polyolefin microporous film and a thermoplastic polymer coating layer covering at least a part of at least one of surfaces of the polyolefin microporous film, in which the thermoplastic polymer coating layer, on the polyolefin microporous film, has a portion containing a thermoplastic polymer and a portion not containing the thermoplastic polymer in a sea-island configuration, the thermoplastic polymer coating layer contains the thermoplastic polymer having at least two glass-transition temperatures, at least one of the glass-transition temperatures is in a range of less than 20° C. and at least one of the glass-transition temperatures is in a range of 20° C. or more.

TECHNICAL FIELD

The present invention relates to a separator for an electricity storagedevice, a laminate and a porous film.

BACKGROUND ART

Recently, development of non-aqueous electrolyte batteries, mainlylithium ion batteries, has been aggressively made. Generally, innon-aqueous electrolyte batteries, a microporous film (separator) isprovided between positive and negative electrodes. The separatorfunctions to prevent direct contact between the positive and negativeelectrodes and passes ions through an electrolytic solution held inmicropores.

In order to improve cycle characteristics and safety of a non-aqueouselectrolyte battery, improvement of a separator has been considered. Forexample, Patent Literature 1 proposes an adhesive porous film, which isproduced by applying a reactive polymer onto a porous film followed bydrying, in order to provide a secondary battery having excellentelectric discharge characteristics and safety.

Recently, in accordance with reduction in size and thickness of portableappliances, it has been required that electricity storage devices suchas a lithium ion secondary battery reduce in size and thickness. Incontrast, in order for portable appliances to be able to carry for along time, increasing capacity of the batteries by improving volumeenergy density has been attempted.

Then, it is required that a separator is improved in adhesiveness toelectrodes in view of not only conventional issues on safetyperformance, such as characteristics (fuse characteristics) ofterminating a battery reaction immediately upon the occurrence ofabnormal heating, and performance (short circuit characteristics) ofmaintaining the shape of the battery even if temperature is elevated toprevent a dangerous situation where a positive-electrode materialdirectly reacts with a negative-electrode material, but also uniformityof charge-discharge current and suppression of lithium dendriteprecipitation.

Nonuniform charge-discharge current and precipitation of lithiumdendrite rarely occur by improving adhesiveness between a separator andbattery electrodes, with the result that the charge-discharge cycle lifecan be extended.

Under the circumstances, to provide adhesiveness to a separator, anattempt to apply an adhesive polymer to a polyolefin microporous filmhas been made (see, for example, Patent Literatures 1 and 2).

CITATION LIST Patent Literature

Patent Literature 1: Japanese Patent Laid-Open No. 2007-59271

Patent Literature 2: Japanese Patent Laid-Open No. 2011-54502

SUMMARY OF INVENTION Technical Problem

The separator of Patent Literature 1, however, has a problem in thatadhesiveness between a reactive polymer and a porous film is notsufficient and accordingly adhesiveness to electrodes is insufficient.The separator has another problem in that if the glass-transitiontemperature (Tg) of the reactive polymer is decreased in order toimprove adhesiveness between the reactive polymer and the porous film,the outermost surface of the separator becomes sticky and handlingperformance decreases.

In both of the microporous films described in Patent Literatures 1 and2, there is still room for improvement in view of handling performanceand adhesiveness in rolling up electrodes, etc. for forming a battery,and lithium ion permeability.

A first embodiment of the present invention was made in view of theaforementioned problems and is directed to provide a separator excellentin adhesiveness to electrodes and a separator for an electricity storagedevice also excellent in handling performance.

A second embodiment of the present invention was made in view of theaforementioned problems and is directed to provide a porous filmexcellent in handling performance at the time of rolling and excellentin rate characteristics of an electricity storage device when the porousfilm is used as the separator for the electricity storage device, andprovide a separator for an electricity storage device formed of theporous film and an electricity storage device using the separator.Another object is to provide a porous film excellent in adhesivenessbetween a thermoplastic polymer and a polyolefin microporous film andpermeability, a separator for an electricity storage device formed ofthe porous film and an electricity storage device using the separator.

Solution to Problem

The present inventors conducted intensive studies with a view toattaining the above objects. As a result, they found that the problemscan be overcome by providing a thermoplastic polymer havingpredetermined thermal characteristics on at least a part of at least oneof the surfaces of a polyolefin microporous film.

More specifically, the present invention is as follows.

[1] A separator for an electricity storage device comprising apolyolefin microporous film and a thermoplastic polymer coating layercovering at least a part of at least one of surfaces of the polyolefinmicroporous film, wherein

the thermoplastic polymer coating layer, on the polyolefin microporousfilm, has a portion containing a thermoplastic polymer and a portion notcontaining the thermoplastic polymer in a sea-island configuration,

the thermoplastic polymer coating layer contains the thermoplasticpolymer having at least two glass-transition temperatures,

at least one of the glass-transition temperatures is in a range of lessthan 20° C., and

at least one of the glass-transition temperatures is in a range of 20°C. or more.

[2] The separator for the electricity storage device according to theabove [1] or [2], wherein, in the thermoplastic polymer coating layer,

a thermoplastic resin having a glass-transition temperature of 20° C. ormore is present on a side of a outermost surface of the separator forthe electricity storage device, and

a thermoplastic resin having a glass-transition temperature of less than20° C. is present on a side of a interface between the polyolefinmicroporous film and the thermoplastic polymer coating layer.

[3] The separator for the electricity storage device according to theabove [1] or [2], wherein a peel strength of an aluminum foil after thealuminum foil is pressed at a temperature of 25° C. and a pressure of 5MPa for 3 minutes against the outermost surface of the separator for theelectricity storage device having the thermoplastic polymer coatinglayer thereon is 8 gf/cm or less.

[4] The separator for the electricity storage device according to anyone of the above [1] to [3], wherein a peel strength of an aluminum foilafter the aluminum foil is pressed at a temperature of 80° C. and apressure of 10 MPa for 3 minutes against the outermost surface of theseparator for the electricity storage device having the thermoplasticpolymer coating layer thereon is 30 gf/cm or more.

[5] The separator for the electricity storage device according to anyone of the above [1] to [4], wherein a 90° peel strength of thepolyolefin microporous film and the thermoplastic polymer coating layeris 6 gf/mm or more.[6] The separator for the electricity storage device according to anyone of the above [1] to [5], wherein, in the thermoplastic polymercoating layer, at least a part of the thermoplastic polymer present onthe outermost surface of the separator for the electricity storagedevice is a particulate thermoplastic polymer.[7] The separator for the electricity storage device according to theabove [6], wherein the particulate thermoplastic polymer has an averageparticle size of 0.01 μm to 0.4 μm.[8] The separator for the electricity storage device according to anyone of the above [1] to [7], wherein an area ratio of the polyolefinmicroporous film covered with the thermoplastic polymer coating layerbased on 100% of a total area of the polyolefin microporous film is 95%or less based on 100% of the total area of the polyolefin microporousfilm.[9] The separator for the electricity storage device according to anyone of the above [1] to [8], wherein the area ratio of the polyolefinmicroporous film covered with the thermoplastic polymer coating layer is50% or less based on 100% of the total area of the polyolefinmicroporous film.[10] A laminate formed by laminating the separator for the electricitystorage device according to any one of the above [1] to [9] andelectrodes.[11] A porous film having a polyolefin microporous film and athermoplastic polymer coating layer covering at least a part of at leastone of surfaces of the polyolefin microporous film, wherein

the thermoplastic polymer coating layer contains a thermoplastic polymerhaving a glass-transition temperature in a range of −10° C. or more and40° C. or less, and

a degree of swelling of the thermoplastic polymer with an electrolyticsolution of 5 times or less.

[12] The porous film according to the above [11], wherein thethermoplastic polymer coating layer has an average thickness of 1.5 μmor less.[13] The porous film according to the above [11] or [12], wherein anarea ratio of the polyolefin microporous film coated with thethermoplastic polymer coating layer is 70% or less based on 100% of atotal area of the polyolefin microporous film.[14] The porous film according to any one of the above [11] to [13],wherein the thermoplastic polymer has a gel fraction of 90% or more.[15] The porous film according to any one of the above [11] to [14],wherein the thermoplastic polymer coating layer, formed on thepolyolefin microporous film, has a portion containing the thermoplasticpolymer and a portion not containing the thermoplastic polymer in asea-island configuration, and

the portion containing the thermoplastic polymer is formed in a dotpattern.

[16] The porous film according to the above [15], wherein the dot has anaverage major axis of 20 to 1000 μm.

Advantageous Effects of Invention

According to the first embodiment of the present invention, it ispossible to provide a separator excellent in adhesiveness to electrodesand a separator for an electricity storage device also excellent inhandling performance.

According to the second embodiment of the present invention, it ispossible to provide a porous film excellent in handling performance atthe time of rolling and excellent in rate characteristics of anelectricity storage device when the porous film is used as the separatorfor the electricity storage device, a separator for an electricitystorage device formed of the porous film and an electricity storagedevice using the separator. It is also possible to provide a porous filmexcellent in adhesiveness between a thermoplastic polymer and apolyolefin microporous film and permeability, a separator for anelectricity storage device formed of the porous film and an electricitystorage device using the separator.

DESCRIPTION OF EMBODIMENTS

Now, embodiments (hereinafter each referred to as “the presentembodiment”) for carrying out the present invention will be morespecifically described below. Note that the present invention is notlimited to the following embodiments and can be modified in various wayswithin the range of the gist and carried out.

First Embodiment [Separator for Electricity Storage Device]

The separator for the electricity storage device (hereinafter alsoreferred to simply as the “separator”) according to the presentembodiment has

a polyolefin microporous film (hereinafter also referred to simply as“the microporous film”) and a thermoplastic polymer coating layercovering at least a part of at least one of surfaces of the polyolefinmicroporous film, in which

the thermoplastic polymer coating layer, on the polyolefin microporousfilm, has a portion containing a thermoplastic polymer and a portion notcontaining the thermoplastic polymer in a sea-island configuration,

the thermoplastic polymer coating layer contains the thermoplasticpolymer having at least two glass-transition temperatures,

at least one of the glass-transition temperatures is in a range of lessthan 20° C. and

at least one of the glass-transition temperatures is in a range of 20°C. or more.

[Thermoplastic Polymer Coating Layer]

The separator for the electricity storage device according to thepresent embodiment has a thermoplastic polymer coating layer covering atleast a part of at least one of the surfaces of the polyolefinmicroporous film.

The thermoplastic polymer coating layer contains the thermoplasticpolymer having at least two glass-transition temperatures. At least oneof the glass-transition temperatures of the thermoplastic polymer is ina range of less than 20° C. and at least one of the glass-transitiontemperatures is in a range of 20° C. or more.

[Thermoplastic Polymer]

Examples of the thermoplastic polymer to be used in the presentembodiment, include, but not particularly limited to, polyolefin resinssuch as polyethylene and polypropylene and α-polyolefin;fluorine-containing resins such as polyvinylidene fluoride andpolytetrafluoroethylene and copolymers containing these; diene polymerscontaining a conjugated diene such as butadiene and isoprene as amonomer unit or copolymers containing these and hydrides of these;acrylic polymers containing e.g., an acrylate and a methacrylate as amonomer unit or copolymer containing these and hydrides of these;rubbers such as an ethylene propylene rubber, a polyvinyl alcohol, and apolyvinyl acetate; cellulose derivatives such as ethyl cellulose, methylcellulose, hydroxyethyl cellulose and carboxymethylcellulose; and resinshaving a melting point and/or glass-transition temperature of 180° C. ormore, such as polyphenylene ether, polysulfone, polyethersulfone,polyphenylene sulfide, polyetherimide, polyamideimide, polyamide andpolyester and mixtures of these. Examples of the monomers that can beused for synthesizing a thermoplastic polymer include a monomer having ahydroxyl group and a sulfonic acid group, a carboxyl group, an amidegroup or a cyano group.

Among these thermoplastic polymers, a diene polymer, an acrylic polymeror a fluorine polymer is preferred since it has excellent bindingproperty to an electrode active material, strength and flexibility.

(Diene Polymer)

The diene polymer, which is not particularly limited, is, for example, apolymer containing a monomer unit obtained by polymerizing a conjugateddiene having conjugated two double bonds, such as butadiene andisoprene. Examples of the conjugated diene monomer include, but notparticularly limited to, 1,3-butadiene, isoprene,2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-pentadiene,2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene and3-butyl-1,3-octadiene. These may be polymerized singly or copolymerized.

The ratio of the monomer unit obtained by polymerizing a conjugateddiene in a diene polymer, which is not particularly limited to, is, forexample, 40 mass % or more, preferably 50 mass % or more and morepreferably 60 mass % or more of the whole diene polymer.

Examples of the above diene polymer include, but not particularlylimited to, homopolymers of a conjugated diene such as polybutadiene andpolyisoprene, and copolymers of a conjugated diene and a copolymerizablemonomer. Examples of the copolymerizable monomer may include, but notparticularly limited to, (meth)acrylate monomers (described later) andthe following monomers (hereinafter also referred to as “othermonomers”).

Examples of the “other monomers” include, but not particularly limitedto, α,β-unsaturated nitrile compounds such as acrylonitrile andmethacrylonitrile; unsaturated carboxylic acids such as acrylic acid,methacrylic acid, itaconic acid and fumaric acid; styrene monomers suchas styrene, chlorostyrene, vinyl toluene, t-butyl styrene, vinylbenzoate, methylvinyl benzoate, vinylnaphthalene, chloromethylstyrene,hydroxymethylstyrene, α-methylstyrene and divinylbenzene; olefins suchas ethylene and propylene; halogen atom-containing monomers such asvinyl chloride and vinylidene chloride; vinyl esters such as vinylacetate, vinyl propionate, vinyl butyrate and vinyl benzoate; vinylethers such as methyl vinyl ether, ethyl vinyl ether and butyl vinylether; vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone,butyl vinyl ketone, hexyl vinyl ketone and isopropenyl vinyl ketone;heterocyclic ring-containing vinyl compounds such as N-vinylpyrrolidone,vinylpyridine and vinyl imidazole; acrylate and/or methacrylatecompounds such as methyl acrylate and methyl methacrylate; hydroxyalkylgroup-containing compounds such as β-hydroxyethyl acrylate andβ-hydroxyethyl methacrylate; and amide monomers such as acrylic amide,N-methylolacrylamide, acrylic amide-2-methylpropane sulfonate. These maybe used alone or in combination of two or more.

(Acrylic Polymer)

The acrylic polymer, which is not particularly limited to, is a polymercontaining a monomer unit obtained by polymerizing preferably a(meth)acrylate monomer.

Note that, the “(meth) acrylic acid” in the present specification refersto an “acrylic acid or a methacrylic acid” and the “(meth)acrylate”refers to an “acrylate or a methacrylate”.

Examples of the (meth)acrylate monomer include, but not particularlylimited to, alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl(meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate,n-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate,hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate,2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth) acrylate, n-tetradecyl (meth)acrylate andstearyl (meth)acrylate; hydroxy group-containing (meth)acrylates such ashydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate andhydroxybutyl (meth) acrylate; amino group-containing (meth)acrylatessuch as aminoethyl (meth)acrylate; and epoxy group-containing(meth)acrylates such as glycidyl (meth) acrylate.

The ratio of the monomer unit obtained by polymerizing a (meth)acrylatemonomer, which is not particularly limited, is, for example, 40 mass %or more, preferably 50 mass % or more and more preferably 60 mass % ormore of the total acrylic polymer. Examples of the acrylic polymerinclude a homopolymer of a (meth)acrylate monomer and a copolymer of a(meth)acrylate monomer and a copolymerizable monomer thereof.

Examples of the copolymerizable monomer include “other monomers”mentioned in the above section “diene polymer” and these may be usedalone or in combination of two or more.

(Fluorine Polymer)

Examples of the fluorine polymer include, but not particularly limitedto, a homopolymer of vinylidene fluoride and a copolymer of vinylidenefluoride and a copolymerizable monomer thereof. The fluorine polymer ispreferred in view of electrochemical stability.

The ratio of the monomer unit obtained by polymerizing a vinylidenefluoride, which is not particularly limited to, is, for example, 40 mass% or more, preferably 50 mass % or more and more preferably 60 mass % ormore.

Examples of the copolymerizable monomer with vinylidene fluorideinclude, but not particularly limited to, fluorine-containing ethylenicunsaturated compounds such as vinyl fluoride, tetrafluoroethylene,trifluorochloroethylene, hexafluoropropylene, hexafluoroisobutylene,perfluoroacrylic acid, perfluoromethacrylic acid and a fluoro alkylester of an acrylic acid or a methacrylic acid; non-fluorine containingethylenic unsaturated compounds such as cyclohexylvinyl ether andhydroxyethyl vinyl ether; and non-fluorine containing diene compoundssuch as butadiene, isoprene and chloroprene.

Of the fluorine polymers, a homopolymer of vinylidene fluoride, avinylidene fluoride/tetrafluoro ethylene copolymer, and a vinylidenefluoride/tetrafluoroethylene/hexafluoropropylene copolymer, etc. arepreferred. A particularly preferable fluorine polymer is a vinylidenefluoride/tetrafluoroethylene/hexafluoropropylene copolymer. Thecomposition of monomers thereof usually consists of 30 to 90 mass % ofvinylidene fluoride, 50 to 9 mass % of tetrafluoroethylene and 20 to 1mass % of hexafluoropropylene. These fluorine resin particles may beused alone or as a mixture of two types or more.

As the monomer to be used for synthesizing the above thermoplasticpolymers, a monomer having a hydroxyl group, a carboxyl group, an aminogroup, a sulfonate group, an amide group or a cyano group can be used.

Examples of the monomer having a hydroxy group include, but notparticularly limited to, a vinyl monomer such as pentenol.

Examples of the monomer having a carboxyl group include, but notparticularly limited to, an unsaturated carboxylic acid having anethylenic double bond such as (meth)acrylic acid and itaconic acid, anda vinyl monomer such as pentenoic acid.

Examples of the monomer having an amino group include, but notparticularly limited to, 2-aminoethyl methacrylate.

Examples of the monomer having a sulfonic acid group include, but notparticularly limited to, vinyl sulfonate, methylvinyl sulfonate,(meth)allyl sulfonate, styrene sulfonate, (meth)acrylic acid-2-ethylsulfonate, 2-acrylic amide-2-methylpropane sulfonate and3-aryloxy-2-hydroxypropane sulfonate.

Examples of the monomer having an amide group include, but notparticularly limited to, an acrylamide, methacrylamide,N-methylolacrylamide and N-methylol methacrylamide.

Examples of the monomer having a cyano group include, but notparticularly limited to, acrylonitrile, methacrylonitrile,α-chloroacrylonitrile and α-cyanoethyl acrylate.

The thermoplastic polymers to be used in the present embodiment may beused alone or as a mixture of two types or more and preferably a mixtureof at least two types of polymers.

(Glass-Transition Temperature of Thermoplastic Polymer)

It is characterized in view of adhesiveness between the separator andelectrodes in that the thermoplastic polymers to be used in the presentembodiment have at least two glass-transition temperatures, at least oneof which is in a range of less than 20° C. and at least one of which isin a range of 20° C. or more. The glass-transition temperature herein isdetermined from a DSC curve obtained by differential scanningcalorimetry (DSC). Note that in the present specification, theglass-transition temperature is sometimes represented by Tg.

Specifically, the glass-transition temperature is determined by anintersection of a linear line, which is extended from the base line on alower temperature side on the DSC curve toward a high temperature side,with a tangent line at a glass-transition inflection point present in astepwise change portion. More specifically, the method described inExamples can be referred to.

The “glass transition” herein refers to a calorimetric change caused inDSC on the endothermic side in accordance with a change of a polymer(test piece) state. Such a calorimetric change is observed as a stepwisechange or a stepwise change in combination with a peak in a DSC curve.

The “stepwise change” is seen in a transit portion of the DSC curveapart from an original base line to a new base line. Note that thestepwise change in combination with a peak is also included.

The “inflection point” refers to a point present in the stepwise changeportion of a DSC curve, in which the slope of the DSC curve takes amaximum value. The “inflection point” can be referred to also as a pointpresent in the stepwise change portion at which a convex shaped curvechanges to a concave shaped curve.

The “peak” refers to a portion of the DSC curve in which curve lineseparates from a base line and returns to the base line, again.

The “base line” refers to a DSC curve within a temperature range whereno transition and reaction of a test piece occur.

In the present embodiment, at least one of the glass-transitiontemperatures of the thermoplastic polymer used herein is present in therange of less than 20° C. Owing to this, excellent adhesiveness to amicroporous film is obtained, with the result that an effect, i.e.,excellent adhesiveness between a separator and electrodes, is exerted.At least one of the glass-transition temperatures of the thermoplasticpolymer used herein is preferably present in the range of 15° C. or lessand more preferably in the range of −30° C. or more and 15° C. or less.

The glass-transition temperature present in the range of less than 20°C., is preferably present just within the range of −30° C. or more and15° C. or less, for the reason that adhesiveness between a thermoplasticpolymer and a microporous film is improved and satisfactory handlingperformance is maintained.

In the present embodiment, at least one of the glass-transitiontemperatures of the thermoplastic polymer used herein is present in therange of 20° C. or more. Owing to this, effects, i.e., excellentadhesiveness between a separator and electrodes and excellent handlingperformance, are exerted. At least one of the glass-transitiontemperatures of the thermoplastic polymer used herein is preferablypresent in the range of 20° C. or more and 120° C. or less and morepreferably in the range of 50° C. or more and 120° C. or less. If theglass-transition temperature is present in the above range, satisfactoryhandling performance can be obtained. In addition, adhesiveness betweenelectrodes and a separator, which is provided by application of pressurein a battery fabrication process, can be improved.

The glass-transition temperature present in the range of 20° C. or moreis preferably present just within the range of 20° C. or more and 120°C. or less and more preferably within the range of 50° C. or more and120° C. or less, for the reason that adhesiveness between athermoplastic polymer and a microporous film is improved andsatisfactory handling performance is maintained.

The thermoplastic polymer having two glass-transition temperatures canbe produced by a method of blending at least two types of thermoplasticpolymers or a method of using a thermoplastic polymer having acore-shell structure; however, the method for producing such athermoplastic polymer is not limited to these. The core-shell structureof a polymer refers to a double structure consisting of a core portionand a shell portion, which are formed of different polymers.

Particularly, owing to a polymer blend and the core-shell structure, apolymer of high glass-transition temperature can be used in combinationwith a polymer of a low glass transition temperature, with the resultthat the entire glass-transition temperature of the thermoplasticpolymers can be controlled. In addition, a plurality of functions can beprovided to the entire thermoplastic polymer. To describe it morespecifically, in the case of the blend, if at least two types ofpolymers such as a polymer having a glass-transition temperature in therange of 20° C. or more and a polymer having a glass-transitiontemperature in the range of less than 20° C. are blended, stickinessresistance and wettability for a polyolefin microporous film can besimultaneously obtained. In the case of blending polymers, the blendingratio of a polymer having a glass-transition temperature in the range of20° C. or more and a polymer having a glass-transition temperature inthe range of less than 20° C. falls within the range of preferably0.1:99.9 to 99.9:0.1, more preferably 5:95 to 95:5, further preferably50:50 to 95:5 and still further preferably 60:40 to 90:10. In the caseof a core-shell structure, if a shell polymer is varied, adhesiveness toand compatibility with other materials such as a polyolefin microporousfilm, can be controlled; whereas, if a polymer constituting a coreportion is adjusted, a polymer can be adjusted for enhanced adhesivenessto electrodes after e.g., hot press. Furthermore, if a high-viscositypolymer is used in combination with a high-elasticity polymer,viscoelasticity can be controlled.

Note that the glass-transition temperature of the shell of athermoplastic polymer having a core-shell structure, which is notparticularly limited, is preferably less than 20° C., more preferably15° C. or less and further preferably −30° C. or more and 15° C. orless. The glass-transition temperature of the core of a thermoplasticpolymer having a core-shell structure, which is not particularlylimited, is preferably 20° C. or more, more preferably 20° C. or moreand 120° C. or less and further preferably 50° C. or more and 120° C. orless.

In the present embodiment, the glass-transition temperature, i.e., Tg,of a thermoplastic polymer can be appropriately controlled, for example,by changing the components and the injection ratio of monomers for usein producing the thermoplastic polymer. More specifically, theglass-transition temperature Tg of a thermoplastic polymer can beroughly estimated based on Tg values (generally shown, for example, in“polymer handbook” (A WILEY-INTERSCIENCE PUBLICATION)) of individualmonomers (Tg values of homopolymers) for use in producing athermoplastic polymer and the blending ratio of the monomers. Todescribe it more specifically, if a copolymer is produced by blendingmonomers such as styrene, methyl methacrylate and acrylonitrile, whichprovide a polymer having Tg of about 100° C., in a high ratio, acopolymer having a high Tg value can be obtained. In contrast, if acopolymer is produced by blending monomers such as butadiene, whichprovides a polymer having Tg of about −80° C., and N-butyl acrylate and2-ethylhexyl acrylate, which provide a polymer having Tg of about −50°C., in a high ratio, a copolymer having a low Tg value can be obtained.

Furthermore, Tg of the polymer can be roughly calculated in accordancewith the FOX formula (the following formula (1)). Note that as theglass-transition temperature of the thermoplastic polymer of the presentapplication, a value measured by a method based on the DSC mentionedabove is employed.

1/Tg=W1/Tg1+W2/Tg2+ . . . +Wi/Tgi+ . . . Wn/Tgn   (1)

(in the formula (1), Tg (K) is Tg of a copolymer; Tgi (K) is Tg of eachmonomer i (homopolymer); and Wi is a mass fraction of each monomer)

(Structure of Thermoplastic Polymer Coating Layer)

In the thermoplastic polymer coating layer, it is preferable that athermoplastic resin having a glass-transition temperature of 20° C. ormore be present on the side of the outermost surface of a separator foran electricity storage device and a thermoplastic resin having aglass-transition temperature of less than 20° C. be present on the sideof the interface between a polyolefin microporous film and athermoplastic polymer coating layer. Note that in the sea-island likethermoplastic polymer coating layer, “the outermost surface” refers tothe surface of a sea-island like thermoplastic polymer coating layer incontact with the electrodes when a separator for an electricity storagedevice and electrodes are laminated. Furthermore, “the interface” refersto the surface of the sea-island like thermoplastic polymer coatinglayer in contact with the polyolefin microporous film.

In the thermoplastic polymer coating layer, the thermoplastic resinhaving a glass-transition temperature of 20° C. or more is present onthe side of the outermost surface of a separator for an electricitystorage device. Owing to this, more excellent adhesiveness to amicroporous film is obtained, with the result that adhesiveness of theseparator and electrodes tends to be excellent. Furthermore, athermoplastic resin having a glass-transition temperature of less than20° C. is present on the side of the interface between the polyolefinmicroporous film and the thermoplastic polymer coating layer. Owing tothis, adhesiveness between the separator and electrodes and handlingperformance tend to be more excellent.

Due to the presence of such a thermoplastic polymer coating layer,adhesiveness between a separator and electrodes and handling performancetend to be more improved. The above structure can be achieved bysatisfying, for example, the following matters: (a) a thermoplasticpolymer consists of a particulate thermoplastic polymer and a binderpolymer, which allows the particulate thermoplastic polymer to adhere toa polyolefin microporous film in such a state that the particulatethermoplastic polymer is exposed on the surface, and theglass-transition temperature of the particulate thermoplastic polymer ispresent in the range of 20° C. or more; whereas, a thermoplastic resinhaving a glass-transition temperature of less than 20° C. is present onthe side of the interface between the polyolefin microporous film andthe thermoplastic polymer coating layer; and (b) the thermoplasticpolymer has a laminate structure, the glass-transition temperature of athermoplastic polymer serving as the outermost surface layer when usedas a separator, is present in the range of 20° C. or more; whereas athermoplastic resin having a glass-transition temperature of less than20° C. is present on the side of the interface between the polyolefinmicroporous film and the thermoplastic polymer coating layer. Note that(b) the thermoplastic polymer may have a laminate structure of polymershaving different Tg values.

(Sea-Island Configuration)

The thermoplastic polymer coating layer, on the polyolefin microporousfilm, has a portion containing the thermoplastic polymer and a portionnot containing the thermoplastic polymer in a sea-island configuration.Examples of the shape of islands in sea, which is not particularlylimited to, include a linear, dot, grid, stripe and hexagonal patterns.Of them, in view of obtaining permeability and uniform adhesiveness toelectrodes, dots are more preferable. Dots indicate that a portioncontaining a thermoplastic polymer and a portion not containing thethermoplastic polymer are in a sea-island configuration on thepolyolefin microporous film. Note that, in the thermoplastic polymercoating layer, a portion containing the thermoplastic polymer may bediscretely present like islands, or conversely, present like acontinuous plane. In the case of discrete islands, the shape of theislands is not particularly limited to; however, the interval of islanddots is preferably 5 μm to 500 μm in order that adhesiveness toelectrodes and cycle characteristics are simultaneously obtained.Furthermore, the size of the dots is not particularly limited; however,the average major axis thereof is preferably 10 μm or more and 1000 μmor less, more preferably 20 μm or more and 800 μm or less, and furtherpreferably 50 μm or more and 500 μm or less in order to obtainadhesiveness to electrodes.

The average major axis of dots of the thermoplastic polymer can becontrolled by varying the polymer concentration of a coating liquid, theamount of a polymer solution coated, coating method and coatingconditions thereof.

(Particulate Thermoplastic Polymer)

In the present embodiment, the structure of a thermoplastic polymer,which is not particularly limited to, is, for example, a single layerstructure, a structure consisting of a particulate thermoplastic polymerand a polymer surrounding at least a part of the particulatethermoplastic polymer, and a laminate structure. In the thermoplasticpolymer coating layer, at least a part of the thermoplastic polymerpresent on the outermost surface of a separator for an electricitystorage device is preferably a particulate thermoplastic polymer. Owingto the presence of such a structure, more excellent adhesiveness betweenthe separator and electrodes and handling performance of the separatortend to be obtained.

The “particulate” herein refers to the state where individualthermoplastic polymer particles are in discrete forms having a contourwhen they are observed under a scanning electron microscope (SEM). Theforms may be long and thin, spherical or poly-angular, etc.

In the present embodiment, the area ratio of the particulatethermoplastic polymer based on the thermoplastic polymer present on theoutermost surface of the separator is not particularly limited to;however, the area ratio is preferably 95% or less and more preferably50% or more and 95% or less. The area ratio S of the particulatethermoplastic polymer based on the thermoplastic polymer present on theoutermost surface of the separator is calculated based on the followingformula:

S (%)=area of particulate thermoplastic polymer÷total area ofthermoplastic polymer present on the outermost surface of separator

where the area of particulate thermoplastic polymer is measured underobservation by SEM (magnification: 30000×) of the outermost surface of aseparator, as later described in Examples.

(Average Particle Size of Thermoplastic Polymer)

The average particle size of a particulate thermoplastic polymer ispreferably 0.01 μm to 1 μm, more preferably 0.05 μm to 0.5 μm andfurther preferably 0.01 μm to 0.4 μm. If the average particle size fallswithin the above range, the particles are satisfactorily dispersed in asolution and the concentration, viscosity and the like of the solutionfor coating can be easily controlled to easily form a uniform packedbed. As a result, adhesiveness to electrodes and cycle characteristicsare more improved and the thickness of a coating film can be easilycontrolled.

(Degree of Swelling of Thermoplastic Polymer with Electrolytic Solution)

In the present embodiment, it is preferable that a thermoplastic polymerbe swellable with an electrolytic solution in view of batterycharacteristics such as cycle characteristics. Provided that the weightof a thermoplastic polymer (A), which is prepared by impregnating adried thermoplastic polymer (or a thermoplastic polymer dispersionsolution) with an electrolytic solution for 3 hours, followed bywashing, is represented by Wa, and the weight of (A) obtained after thethermoplastic polymer (A) is allowed to stand still in an oven of 150°C. for one hour is represented by Wb, degree of swelling with theelectrolytic solution can be calculated in accordance with the followingformula. The degree of swelling is preferably 5 times or less, morepreferably 4.5 times or less and further preferably 4 times or less.Furthermore, the degree of swelling is preferably equivalent or more andmore preferably twofold or more.

Degree of swelling of thermoplastic polymer with electrolytic solution(times)=(Wa−Wb)+Wb

In the present embodiment, degree of swelling of a thermoplastic polymerwith an electrolytic solution can be controlled by varying the types andratio of monomers to be polymerized.

(Gel Fraction of Thermoplastic Polymer)

In the present embodiment, the gel fraction of thermoplastic polymer isnot particularly limited; however, the gel fraction is preferably 80% ormore, more preferably 85% or more and further preferably 90% or more inorder to suppress dissolution of the thermoplastic polymer in anelectrolytic solution and maintain strength of the thermoplastic polymerin a battery. The gel fraction herein can be obtained based onmeasurement of toluene-insoluble matter as later described in Examples.

The gel fraction can be controlled by varying the types and ratio ofmonomers to be polymerized and polymerization conditions.

(Content of Thermoplastic Polymer)

In the present embodiment, the content of a thermoplastic polymer, whichis not particularly limited, is preferably 0.05 g/m² or more and 1.0g/m² or less in order to improve adhesion force of separator andsuppress reduction in cycle characteristics (permeability) caused byclogging of the pores of the polyolefin microporous film. The content ismore preferably 0.07 g/m² or more and 0.8 g/m² or less and furtherpreferably 0.1 g/m² or more and 0.7 g/m² or less.

The content of a thermoplastic polymer can be controlled by varying thepolymer concentration of a coating liquid and the amount of polymersolution coated.

(Thickness of Thermoplastic Polymer Coating Layer)

In the present embodiment, the average thickness of a thermoplasticpolymer coating layer on one of the surfaces is preferably 1.5 μm orless, more preferably 1.0 μm or less and further preferably 0.5 μm orless. The average thickness of the thermoplastic polymer is preferably1.5 μm or less. This is because reduction in permeability by thethermoplastic polymer and adhesiveness between thermoplastic polymers orbetween the thermoplastic polymer and a polyolefin microporous film canbe effectively suppressed.

The average thickness of a thermoplastic polymer can be controlled byvarying the polymer concentration of a coating liquid, the amount ofpolymer solution coated, the coating method and coating conditionsthereof.

The thickness of a thermoplastic polymer coating layer can be measuredby the method described in Examples.

(Area Ratio of Polyolefin Microporous Film Covered with ThermoplasticPolymer Coating Layer)

The separator according to the present embodiment has a thermoplasticpolymer in at least a part of at least one of the surfaces of apolyolefin microporous film. The area ratio (%) of the polyolefinmicroporous film covered with the thermoplastic polymer coating layer ispreferably 95% or less, more preferably 70% or less, further preferably50% or less, further preferably 45% or less, and still furtherpreferably 40% or less based on the total area (100%) of the polyolefinmicroporous film. Furthermore, the area ratio (%) is preferably 5% ormore. If the area ratio is 95% or less, blocking of the pores of apolyolefin microporous film with a thermoplastic polymer can be moresuppressed and permeability tends to be more improved. In contrast, ifthe area ratio is 5% or more, adhesiveness tends to be more improved.The area ratio herein, is calculated by a method later described inExamples.

The area ratio can be controlled by varying the polymer concentration ofa coating liquid, the amount of polymer solution coated, the coatingmethod and coating conditions thereof.

[Polyolefin Microporous Film]

In the present embodiment, the polyolefin microporous film, which is notparticularly limited to, is, for example, a porous film formed of apolyolefin resin composition containing a polyolefin and preferably aporous film containing a polyolefin resin as a main component. In thepolyolefin microporous film of the present embodiment, the content of apolyolefin resin is not particularly limited. In view of shutdownperformance in the case where the polyolefin microporous film is used asthe separator for the electricity storage device, the porous film ispreferably formed of a polyolefin resin composition in which apolyolefin resin has a mass fraction of 50% or more and 100% or less ofthe total components constituting the porous film. The percentage of apolyolefin resin is preferably 60% or more and 100% or less and morepreferably 70% or more and 100% or less.

The polyolefin resin, which is not particularly limited, refers to apolyolefin resin for use in usual extrusion, injection, inflation andblow molding, etc. Examples of the polyolefin resin that can be usedinclude homopolymers, copolymers and multi-step polymerization polymersof ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and1-octene, etc. Polyolefins selected from the group consisting ofhomopolymers, copolymers and multi-step polymerization polymers can beused alone or as a mixture.

Typical examples of the polyolefin resin include, but not particularlylimited to, a low-density polyethylene, a linear low-densitypolyethylene, a medium-density polyethylene, a high-densitypolyethylene, an ultrahigh molecular weight polyethylene, an isotacticpolypropylene, an atactic polypropylene, an ethylene-propylene randomcopolymer, a polybutene and an ethylene propylene rubber.

In the case where the separator of the present embodiment is used as abattery separator, in particular, a resin containing a high-densitypolyethylene as a main component is preferably used since it has a lowmelting point and high strength.

In order to improve the heat resistance of a porous film, a porous filmformed of a resin composition containing a polypropylene and apolyolefin resin except the polypropylene is more preferably used.

The tertiary structure of the polypropylene herein is not limited andany of an isotactic polypropylene, a syndiotactic polypropylene and anatactic polypropylene may be used.

The ratio of a polypropylene based on the total polyolefin in apolyolefin resin composition, which is not particularly limited to, ispreferably 1 to 35 mass %, more preferably 3 to 20 mass % and furtherpreferably 4 to 10 mass % in order to simultaneously obtain heatresistance and satisfactory shutdown function.

In this case, examples of the polyolefin resin except the polypropylene,include, but not limited to, an olefin hydrocarbon homopolymer orcopolymer such as ethylene, 1-butene, 4-methyl-1-pentene, 1-hexene and1-octene. Specific examples thereof include polyethylene, polybutene andan ethylene-propylene random copolymer.

In view of shutdown characteristics (pores are blocked by thermofusion),as the polyolefin resin except the polypropylene, a polyethylene such asa low-density polyethylene, a linear low-density polyethylene, amedium-density polyethylene, a high-density polyethylene and anultrahigh molecular weight polyethylene is preferably used. Among these,in view of strength, a polyethylene having a density of 0.93 g/cm³ ormore, which is measured in accordance with JISK7112, is more preferablyused.

The viscosity average molecular weight of a polyolefin resinconstituting a polyolefin microporous film, which is not particularlylimited to, is preferably 30,000 or more and 12,000,000 or less, morepreferably 50,000 or more and less than 2,000,000 and further preferably100,000 or more and less than 1,000,000. The viscosity average molecularweight is preferably 30,000 or more. This is because, if so, the melttension in a melt-molding process increases and satisfactory moldabilityis obtained; at the same time, strength tends to increase since polymerchains get tangled. In contrast, the viscosity average molecular weightis preferably 12,000,000 or less. This is because, if so, uniformmelt-kneading can be easily made and the resultant sheet tends to hasexcellent moldability, particularly thickness stability. Furthermore,the viscosity average molecular weight is preferably less than1,000,000. This is because, if so, pores tend to be easily blocked astemperature increases and satisfactory shutdown function tends to beobtained. Note that in place of solely using a polyolefin having aviscosity average molecular weight of, for example, less than 1,000,000,a mixture of a polyolefin having a viscosity average molecular weight of2,000,000 and a polyolefin having a viscosity average molecular weightof 270,000 and having a viscosity average molecular weight of less than1,000,000 may be used.

In the present embodiment, the polyolefin microporous film can containadditives, if necessary. Examples of the additives include, but notparticularly limited to, a polymer except a polyolefin; an inorganicparticle; an antioxidant such as a phenol based, phosphorus based, andsulfur based antioxidants; a metallic soap such as calcium stearate andzinc stearate; a UV absorber; a light stabilizer; an antistatic agent;an antifog additive; and a color pigment.

The total content of these additives is preferably at most 20 parts bymass, more preferably at most 10 parts by mass and further preferably atmost 5 parts by mass based on the polyolefin resin composition (100parts by mass).

(Physical Properties of Polyolefin Microporous Film)

In the present embodiment, puncture strength of the polyolefinmicroporous film, which is not particularly limited to, is preferably200 g/20 μm or more, more preferably 300 g/20 μm or more; and preferably2000 g/20 μm or less and more preferably 1000 g/20 μm or less. Thepuncture strength is preferably 200 g/20 μm or more in order to suppressfilm breakage by e.g., an active material dropped out during rolling upa battery and also to suppress a fear of short-circuit caused byexpansion-contraction of an electrode in accordance with electriccharge-discharge. In contrast, a puncture strength is preferably 2000g/20 μm or less because width contraction due to orientationalrelaxation during heating can be reduced. The puncture strength hereinis measured by a method later described in Examples.

Note that the above puncture strength can be controlled by, for example,controlling stretching ratio and stretching temperature.

In the present embodiment, the porosity of a polyolefin microporousfilm, which is not particularly limited to, is preferably 20% or moreand more preferably 35% or more; and preferably 90% or less and morepreferably 80% or less. The porosity is preferably 20% or more in orderto obtain the permeability of a separator. In contrast, the porosity ispreferably 90% or less in order to obtain puncture strength. Theporosity herein is measured by a method later described in Examples.

Note that the porosity can be controlled by varying e.g., a stretchingratio.

In the present embodiment, the thickness of a polyolefin microporousfilm, which is not particularly limited to, is preferably 2 μm or moreand more preferably 5 μm or more; and preferably 100 μm or less, morepreferably 60 μm or less and further preferably 50 μm or less. The filmthickness is preferably 2 μm or more in order to improve machinestrength. In contrast, the film thickness is preferably 100 μm or lesssince the volume occupied by the separator reduces, which tends to beadvantageous in increasing capacity of a battery.

In the present embodiment, the air permeability of a polyolefinmicroporous film, which is not particularly limited to, is preferably 10sec/100 cc or more and more preferably 50 sec/100 cc or more; andpreferably 1000 sec/100 cc or less and more preferably 500 sec/100 cc orless. The air permeability is preferably 10 sec/100 cc or more since theself-discharge of an electricity storage device is suppressed. Incontrast, the air permeability is preferably 1000 sec/100 cc or lesssince satisfactory charge-discharge characteristics are obtained. Theair permeability herein is measured by a method later described inExamples.

Note that the air permeability can be controlled by varying e.g.,stretching temperature and stretching ratio.

In the present embodiment, the average pore diameter of a polyolefinmicroporous film is preferably 0.15 μm or less and more preferably 0.1μm or less; and the lower limit of the average pore diameter ispreferably 0.01 μm or more. The average pore diameter is preferably 0.15μm or less since the self-discharge of the electricity storage deviceand capacity drop are suppressed in the case where the polyolefinmicroporous film is used as the separator for the electricity storagedevice. The average pore diameter can be controlled by e.g., varying thestretching ratio when the polyolefin microporous film is produced.

In the present embodiment, short-circuit temperature, which is used asan index of heat resistance of a polyolefin microporous film, ispreferably 140° C. or more, more preferably 150° C. or more and furtherpreferably 160° C. or more. The short-circuit temperature is preferably140° C. or more in view of safety of an electricity storage device whenthe polyolefin microporous film is used as a separator for theelectricity storage device.

(Method for Manufacturing a Polyolefin Microporous Film)

In the present embodiment, a method for producing a polyolefinmicroporous film is not particularly limited to, and a manufacturingmethod known in the art can be employed. Examples of such a methodinclude a method of forming a porous film by melt-kneading a polyolefinresin composition and a plasticizer, molding the kneaded product into asheet, followed by stretching, as necessary, and then extracting theplasticizer; a method of forming a porous film by melt-kneading apolyolefin resin composition, extruding the kneaded product at a highdraw ratio, followed by heating and stretching to peel a polyolefincrystal interface; a method of forming a porous film by melt-kneading apolyolefin resin composition and an inorganic filler, molding thekneaded product into a sheet, followed by stretching to peel theinterface between the polyolefin and the inorganic filler; and a methodof forming a porous film by dissolving a polyolefin resin composition,thereafter soaking in a poor solvent for the polyolefin to coagulate thepolyolefin; at the same time, remove the solvent.

As an example of the method for producing a porous film, a method offorming a porous film by melt-kneading a polyolefin resin compositionand a plasticizer, molding the kneaded product into a sheet, and thenextracting the plasticizer will be described below.

First, a polyolefin resin composition and a plasticizer aremelt-kneaded. Examples of the melt-kneading method include a method ofloading a polyolefin resin and if necessary, other additives in a resinkneading apparatus such as an extruder, a kneader, a laboplastomill,kneading roll and Bambari mixer, adding a plasticizer at an arbitraryratio and kneading the mixture while melting a resin component withheat. At this time, before the polyolefin resin, other additives andplasticizer are loaded into the resin kneading apparatus, they arepreferably preparatorily blended in a predetermined ratio and kneaded inadvance by e.g., a Henschel mixer. More preferably, in the preparatorykneading step, only a part of the plasticizer is loaded and kneading isperformed by the resin kneading apparatus while side-feeding theremaining plasticizer. In this way, dispersibility of the plasticizer isimproved and a sheet compact, which is a melt-kneaded product of a resincomposition and a plasticizer, can be stretched at a high rate withoutfilm breakage in a later step.

As the plasticizer, a nonvolatile solvent, which can produce a uniformsolution of a polyolefin at a temperature of the melting point orhigher, can be used. Specific examples of such a nonvolatile solventinclude, hydrocarbons such as liquid paraffin and paraffin wax; esterssuch as dioctyl phthalate and dibutyl phthalate; and higher alcoholssuch as oleyl alcohol and stearyl alcohol. Among these, liquid paraffinis preferable since it has high compatibility with a polyethylene and apolypropylene and interfacial peeling between a resin and a plasticizerrarely occurs even if a melt-kneaded product is stretched, with theresult that uniform stretching tends to be easily made.

The ratio of a polyolefin resin composition and a plasticizer is notparticularly limited to as long as they can uniformly melt-kneaded andmolded into a sheet. For example, the mass fraction of a plasticizer ina composition composed of a polyolefin resin composition and theplasticizer is preferably 30 to 80 mass % and more preferably 40 to 70mass %. If the mass fraction of a plasticizer is 80 mass % or less, melttension during melt processing rarely reduces and moldability tends tobe improved. In contrast, if the mass fraction is 30 mass % or more,even if a mixture of a polyolefin resin composition and a plasticizer isstretched at a high ratio, a polyolefin chain will not break. Inaddition, micro-pore structures are uniformly formed and strength iseasily increased.

Subsequently, a melt-kneaded product is molded into a sheet. As a methodfor producing a sheet compact, for example, a method for producing asheet compact by extruding a melt-kneaded product, via e.g., a T-die,into a sheet and allowing the sheet in contact with a thermo-conductingbody to cool it to a temperature sufficiently lower than thecrystallization temperature of a resin component and solidify it. As thethermo-conducting body to be used for cooling to solidify, e.g., ametal, water, air or a plasticizer itself can be used; however, a metalroll is preferred since it has a high thermal conduction efficiency. Atthe time when a sheet is brought into contact with a metal roll, thesheet is more preferably sandwiched between rolls. This is because, ifso, the thermal conduction efficiency is further improved; at the sametime, the sheet is oriented to increase film strength and improvesurface smoothness of the sheet. The die-lip interval when amelt-kneaded product is extruded into a sheet via a T die, is preferably400 μm or more and 3000 μm or less and further preferably 500 μm or moreand 2500 μm or less. If the die-lip interval is 400 μm or more, e.g.,drool is reduced, film quality is less affected by defects such asstripes, with the result that occurrence of film breakage or the like inthe following stretching step tends to be prevented. In contrast, if thedie-lip interval is 3000 μm or less, a cooling rate is high, with theresult that nonuniform cooling can be prevented and the thicknessstability of sheet tends to be maintained.

The sheet compact thus obtained is preferably stretched. As a stretchingprocess, either monoaxial stretching or biaxial stretching can bepreferably used; however, biaxial stretching is preferable in view ofe.g., strength of the porous film obtained. If the sheet compact isbiaxially stretched at a high stretching ratio, molecules are orientedin a planar direction and the porous film finally obtained is rarelybroken and has a high puncture strength. Examples of the stretchingmethod include simultaneous biaxial stretching, sequential biaxialstretching, multi-stage stretching and multi-time stretching. In view ofimprovement of puncture strength, uniformity of stretching and shutdownproperties, the simultaneous biaxial stretching is preferred.

Note that the simultaneous biaxial stretching herein refers to astretching method in which stretching in the MD (machine direction of amicroporous film) and stretching in the TD (direction crossed at anangle of 90° with the MD of a microporous film) are simultaneouslyapplied. The stretching ratios of individual directions may differ. Thesequential biaxial stretching refers to a stretching method in whichstretching in the MD or TD is independently carried out. When stretchingof one of the directions of MD and TD is carried out, the otherdirection is placed in an unrestrained condition or fixed so as to havea constant length.

The stretching ratio falls preferably within the range of 20 times ormore and 100 times or less in terms of an area stretching ratio, furtherpreferably within the range of 25 times or more and 50 times or less. Asthe stretching ratios of individual directions, the stretching ratio inthe MD preferably falls within the range of 4 times or more and 10 timesor less; whereas the stretching ratio in the TD preferably falls withinthe range of 4 times or more and 10 times or less; and the stretchingratio in the MD more preferably falls within the range of 5 times ormore and 8 times or less; whereas, the stretching ratio in the TD morepreferably falls within the range of 5 times or more and 8 times orless. If the total area ratio is 20 times or more, the porous film to beobtained tends to successfully have sufficient strength. In contrast, ifthe total area ratio is 100 times or less, film breakage in a stretchingstep can be prevented and high productivity tends to be successfullyobtained.

The sheet compact may be rolled. The rolling can be carried out, forexample, by a pressing method using e.g., a double belt pressingmachine. The orientation of particularly a surface-layer portion can beincreased by rolling. The rolling area ratio is preferably larger thanthe equivalent to 3 times or less and more preferably larger than theequivalent to 2 times or less. If the rolling ratio is larger than theequivalent, the degree of orientation of the plane increases and thestrength of the porous film finally obtained tends to increase. Incontrast, the rolling ratio is preferably 3 times or less. This isbecause, if so, the difference in the degree of orientation between thesurface-layer portion and the interior center is low, a porous structureuniform in a film-thickness direction tends to be successfully formed.

Subsequently, the plasticizer is removed from the sheet compact to forma porous film. Examples of a method for removing a plasticizer include amethod of extracting a plasticizer by soaking a sheet compact in anextraction solvent, followed by sufficient drying. The method ofextracting a plasticizer may be carried out in a batch process or acontinuous process. To suppress contraction of the porous film, the endsof the sheet compact are preferably fixed in soaking and drying steps.Furthermore, the remaining amount of plasticizer in the porous film ispreferably less than 1 mass %.

As the extraction solvent, a solvent serving as a poor solvent for apolyolefin resin and a good solvent for a plasticizer and having aboiling point lower than the melting point of the polyolefin resin ispreferably used. Examples of such an extraction solvent includehydrocarbons such as n-hexane and cyclohexane; halogenated hydrocarbonssuch as dichloromethane and 1,1,1-trichloroethane; non-chlorine basedhalogenated solvents such as hydrofluoroether and hydrofluorocarbon;alcohols such as ethanol and isopropanol; ethers such as diethyletherand tetrahydrofuran; and ketones such as acetone and methyl ethylketone. Note that these extraction solvents may be recovered by anoperation such as distillation and put in recycle use.

To suppress contraction of a porous film, a heat treatment such as heatsetting and thermal relaxation may be applied to the porous film after astretching step or after the porous film is formed. Furthermore, a posttreatment such as a hydrophilization treatment with a surfactant or thelike and a crosslinking treatment with ionizing radiation or the likemay be applied to a porous film.

[Porous Layer]

Furthermore, the separator for the electricity storage device accordingto the present embodiment may have a porous layer containing aninorganic filler and a resin binder. The position of the porous layermay be at least a part of a surface of a polyolefin microporous film, atleast a part of a surface of a thermoplastic polymer coating layerand/or between the polyolefin microporous film and the thermoplasticpolymer coating layer. The porous layer may be present on one or bothsurfaces of the polyolefin microporous film.

(Inorganic Filler)

The inorganic filler to be used in the porous layer is not particularlylimited to; however, an inorganic filler having a melting point of 200°C. or more and a high electric insulating property and beingelectrochemically stable within the application range of a lithium ionsecondary battery is preferable.

Examples of the inorganic filler include, but not particularly limitedto, oxide ceramics such as alumina, silica, titania, zirconia, magnesia,ceria, yttria, zinc oxide and iron oxide; nitride ceramics such assilicon nitride, titanium nitride and boron nitride; ceramics such assilicon carbide, calcium carbonate, magnesium sulfate, aluminiumsulfate, aluminium hydroxide, aluminum hydroxide oxide, potassiumtitanate, talc, kaolinite, dickite, nacrite, halloysite, pyrophyllite,montmorillonite, sericite, mica, amesite, bentonite, asbestos, zeolite,calcium silicate, magnesium silicate, diatomaceous earth and silicasand; and glass fiber. These may be used alone or in combination.

Of them, in order to improve electrochemical stability andheat-resisting property of a multilayer porous film, an aluminum oxidecompound such as alumina and aluminum hydroxide oxide and an aluminiumsilicate compound having no ion-exchange capacity, such as kaolinite,dickite, nacrite, halloysite and pyrophyllite, are preferable. As thealuminum oxide compound, an aluminum hydroxide oxide is particularlypreferable. As the aluminium silicate compound having no ion exchangecapacity, kaolin mainly constituted of a kaolin mineral, is morepreferable since it is inexpensive and easily available. Examples of thekaolin include wet kaolin and fired kaolin obtained by baking wetkaolin. The fired kaolin is particularly preferable in view ofelectrochemical stability since crystallization water is released aswell as impurities are removed in a baking treatment.

The average particle size of the inorganic filler is preferably morethan 0.1 μm and 4.0 μm or less, more preferably more than 0.2 μm and 3.5μm or less and further preferably more than 0.4 μm and 3.0 μm or less.It is preferable to control the average particle size of the inorganicfiller within the above range since even if the porous layer is thin(for example, 7 μm or less), thermal contraction at a high temperaturecan be suppressed.

In the inorganic filler, the ratio of particles having a size of morethan 0.2 μm and 1.4 μm or less based on the entire inorganic filler ispreferably 2 vol % or more, more preferably 3 vol % or more and furtherpreferably 5 vol % or more. The upper limit thereof is preferably 90 vol% or less and more preferably 80 vol % or less.

In the inorganic filler, the ratio of particles having a size of morethan 0.2 μm and 1.0 μm or less based on the entire inorganic filler ispreferably 1 vol % or more and more preferably 2 vol % or more. Theupper limit thereof is preferably 80 vol % or less and more preferably70 vol % or less.

In the inorganic filler, the ratio of particles having a size of morethan 0.5 μm and 2.0 μm or less based on the entire inorganic filler ispreferably 8 vol % or more and more preferably 10 vol % or more. Theupper limit thereof is preferably 60 vol % or less and more preferably50 vol % or less.

In the inorganic filler, the ratio of particles having a size of morethan 0.6 μm and 1.4 μm or less based on the entire inorganic filler ispreferably 1 vol % or more and more preferably 3 vol % or more. Theupper limit thereof is preferably 40 vol % or less and more preferably30 vol % or less.

It is preferable that the particle size distribution of the inorganicfiller be controlled within the above range since even if the porouslayer is thin (for example, 7 μm or less), thermal contraction at a hightemperature can be suppressed. Examples of a method for controlling theratio of the size of the inorganic filler particle include a method ofreducing the size of the particle by pulverizing the inorganic filler byuse of a ball mill, a bead mill, a jet mill or the like.

Examples of shape of the inorganic filler include a tabular, scale-like,needle, columnar, spherical, polyhedron shapes and massive form.Inorganic fillers having the above shapes may be used in combination.The shape of the inorganic filler is not particularly limited to as longas the thermal contraction (described later) of a multilayer porous filmformed of the inorganic filler at 150° C. can be suppressed within 10%or less. A polyhedron shape formed of a plurality of planes, a columnarshape and a spindle shape are preferable in view of improvingpermeability.

The ratio of the inorganic filler in the porous layer can beappropriately determined in view of the binding property of theinorganic filler, the permeability and heat resistance of a multilayerporous film, etc. The ratio is preferably 50 mass % or more and lessthan 100 mass %, more preferably 70 mass % or more and 99.99 mass % orless, further preferably 80 mass % or more and 99.9 mass % or less andparticularly preferably 90 mass % or more and 99 mass % or less.

(Resin Binder)

The type of resin binder is not particularly limited to. If themultilayer porous film of the present embodiment is used as a separatorfor a lithium ion secondary battery, it is preferable to use a resinbinder insoluble in an electrolytic solution of a lithium ion secondarybattery and electrochemically stable in the application range of thelithium ion secondary battery.

Specific examples of the resin binder include polyolefins such as apolyethylene and a polypropylene; fluorine-containing resins such aspolyvinylidene fluoride and polytetrafluoroethylene; fluorine-containingrubbers such as a vinylidenefluoride-hexafluoropropylene-tetrafluoroethylene copolymer and anethylene-tetrafluoroethylene copolymer; rubbers such as astyrene-butadiene copolymer and a hydride thereof, anacrylonitrile-butadiene copolymer and a hydride thereof, anacrylonitrile-butadiene-styrene copolymer and a hydride thereof, amethacrylate-acrylate copolymer, a styrene-acrylate copolymer, anacrylonitrile-acrylate copolymer, an ethylene propylene rubber, apolyvinyl alcohol and polyvinyl acetate; cellulose derivatives such asethylcellulose, methylcellulose, hydroxyethylcellulose andcarboxymethylcellulose; and resins having a melting point and/or aglass-transition temperature of 180° C. or more, such as polyphenyleneether, polysulfone, polyethersulfone, polyphenylene sulfide,polyetherimide, polyamide-imide, polyamide and polyester.

In the case where a polyvinyl alcohol is used as a resin binder, thesaponification degree thereof is preferably 85% or more and 100% orless. The saponification degree is preferably 85% or more. This isbecause, if so, when a multilayer porous film is used as a separator forbattery, the temperature (short-circuit temperature), at which a shortcircuit occurs, increases and more satisfactory safe performance tendsto be successfully obtained. The saponification degree is morepreferably 90% or more and 100% or less, further preferably 95% or moreand 100% or less and particularly preferably 99% or more and 100% orless. Furthermore, the polymerization degree of a polyvinyl alcohol ispreferably 200 or more and 5000 or less, more preferably 300 or more and4000 or less and further preferably 500 or more and 3500 or less. Thepolymerization degree is preferably 200 or more. This is because, if so,an inorganic filler such as fired kaolin, can be allowed to tightlyadhere to a porous film with a small amount of polyvinyl alcohol and airpermeability of the multilayer porous film tends to be successfullysuppressed from increasing due to the formation of a porous layer whilemaintaining the mechanical strength of the porous layer. In contrast,the polymerization degree is preferably 5000 or less. This is because,if so, e.g., gelatinization in preparing a coating liquid tends to besuccessfully prevented.

As the resin binder, a latex binder formed of a resin is preferable. Ifa latex binder formed of a resin is used, more specifically, if a porouslayer containing an inorganic filler and the binder is laminated on atleast one surface of a porous polyolefin film, ion permeability rarelyreduces and high output characteristics tend to be easily obtained,compared to the case of binding a resin binder to a porous film by, forexample, dissolving a whole or part of the resin binder in a solvent,applying the obtained solution to at least one surface of a porouspolyolefin film to obtain a laminate and removing the solvent by soakingthe laminate into a poor solvent or drying the laminate. In addition,also in the case where temperature rapidly increases during abnormalheat generation, smooth shutdown characteristics are obtained and highsafety tends to be easily obtained.

As the latex binder formed of a resin, in order to improveelectrochemical stability and binding property, binders obtained byemulsion polymerization of an aliphatic conjugated diene monomer and anunsaturated carboxylic acid monomer with other monomers copolymerizablewith these are preferred. As an emulsion polymerization method, which isnot particularly limited to, a conventionally known method can be used.As a method for adding monomers and other components, which is notparticularly limited to, any one of a simultaneous addition method, astepwise addition method and a continuous addition method can beemployed. Furthermore, any one of a one-step polymerization, two-steppolymerization or a multi-stage polymerization can be employed.

Examples of the aliphatic conjugated diene monomer, include, but notparticularly limited to, 1,3-butadiene, 2-methyl-1,3-butadiene,2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, substituted linearconjugated pentadienes and a substituted and side-chain conjugatedhexadienes. These may be used alone or in combination of two or more. Ofthe aforementioned ones, particularly, 1,3-butadiene is preferable.

Examples of the unsaturated carboxylic acid monomer include, but notparticularly limited to, mono or dicarboxylic acids (anhydrides) such asacrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acidand itaconic acid. These may be used alone or in combination of two ormore. Of the aforementioned ones, particularly, acrylic acid andmethacrylic acid are preferable.

Examples of the other monomers copolymerizable with these include, butnot particularly limited to, an aromatic vinyl monomer, a vinyl cyanidemonomer, an unsaturated alkyl carboxylate monomer, an unsaturatedmonomer having a hydroxyalkyl group and an unsaturated carboxylic acidamide monomer. These may be used alone or in combination of two or more.Of the aforementioned ones, particularly, an unsaturated alkylcarboxylate monomer is preferable. Examples of the unsaturated alkylcarboxylate monomer include, but not particularly limited to, methylacrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butylacrylate, glycidyl methacrylate, dimethyl fumarate, diethyl fumarate,dimethyl maleate, diethyl maleate, dimethyl itaconate, monomethylfumarate, monoethyl fumarate and 2-ethylhexyl acrylate. These may beused alone or in combination of two or more. Of the aforementioned ones,particularly, methyl methacrylate is preferable.

Note that in addition to these monomers, monomer components other thanthe aforementioned ones can be further used in order to improve variousqualities and physical properties.

The average particle size of a resin binder is preferably 50 to 500 nm,more preferably 60 to 460 nm and further preferably 80 to 250 nm. If theaverage particle size of a resin binder is 50 nm or more, when a porouslayer containing an inorganic filler and a binder is laminated on atleast one surface of a porous polyolefin film, ion permeability rarelyreduces and high output characteristics are easily obtained. Inaddition, in the case where temperature rapidly increases duringabnormal heat generation, smooth shutdown characteristics are obtainedand high safety can be easily obtained. If the average particle size ofa resin binder is 500 nm or less, satisfactory binding property isexpressed. When a multilayer porous film formed by using the resinbinder is used, thermal contraction becomes satisfactory and excellentsafety tends to be obtained.

The average particle size of a resin binder can be controlled bycontrolling e.g., polymerization time, polymerization temperature,composition ratio of starting materials, the order of injecting startingmaterials and pH.

The thickness of a porous layer is preferably 1 μm or more in order toimprove heat resistance and insulating property, and preferably 50 μm orless in order to increase the capacity of a battery and improvepermeability thereof. The thickness of a porous layer is more preferably1.5 μm or more and 20 μm or less, further preferably 2 μm or more and 10μm or less, further more preferably 3 μm or more and 10 μm or less andparticularly preferably 3 μm or more and 7 μm or less.

The density of a porous layer is preferably 0.5 to 2.0 g/cm³ and morepreferably 0.7 to 1.5 g/cm³. If the density of a porous layer is 0.5g/cm³ or more, a thermal contraction rate at a high temperature tends tobe satisfactory; whereas if the density of a porous layer is 2.0 g/cm³or less, air permeability tends to reduce.

Examples of a method for forming a porous layer include a method ofapplying a coating liquid containing an inorganic filler and a resinbinder onto at least one surface of a porous film containing apolyolefin resin as a main component to form a porous layer.

As a solvent for the coating liquid, a solvent that can uniformly andstably disperse the inorganic filler and the resin binder is preferable.Examples thereof include N-methylpyrrolidone, N,N-dimethylformamide,N,N-dimethylacetamide, water, ethanol, toluene, hot xylene,dichloromethane and hexane.

In order to improve dispersion stability and applicability, variousadditives including a dispersant such as a surfactant, a thickener, awetting agent, a defoaming agent and a pH moderator including an acidand an alkali may be added to the coating liquid. These additives arepreferably removed when a solvent is removed; however, they may remainwithin a porous layer as long as they are electrochemically stable, donot inhibit a battery reaction and are stable up to about 200° C. in theapplication range of a lithium ion secondary battery.

A method for dispersing the inorganic filler and the resin binder in asolvent of a coating liquid is not particularly limited as long asdispersion characteristics of a coating liquid required for a coatingstep can be realized. Examples of a mechanical stirring method include aball mill, a bead mill, a planetary ball mill, a vibratory ball mill, asand mill, a colloidal mill, an attritor, a roll mill, high-speedimpeller dispersion, a disperser, homogenizer, a high-velocity impactmill, ultrasonic dispersion or a stirring vane.

A method for applying a coating liquid to a porous film is notparticularly limited as long as the layer-thickness and coating arearequired can be attained. Examples of the method include a gravurecoater method, a small-diameter gravure coater method, a reverse rollcoater method, a transfer roll coater method, a kiss-coater method, adip coater method, a knife coater method, an air doctor coater method, ablade-coater method, a rod coater method, a squeeze coater method, acast coater method, a die coater method, a screen printing method and aspray coating method.

It is preferable that a surface treatment be applied to a surface of aporous film prior to application of a coating liquid. This is because,if so, the coating liquid can be easily applied; at the same time,adhesiveness of an inorganic filler-containing porous layer aftercoating to a porous film surface is improved. A surface treatment methodis not particularly limited as long as the method does not significantlydamage the porous structure of the porous film. Examples of the methodinclude a corona discharge treatment method, a mechanical rough-surfacetreatment method, a solvent treatment method, an acid treatment methodand an ultraviolet oxidation method.

A method for removing a solvent from the coating film after coating isnot particularly limited as long as a porous film is not negativelyaffected. Examples of the method include a method of drying a porousfilm at its melting point or less while immobilizing the porous film anda method of drying the film under reduced pressure. In order to controlcontraction stress in the MD of a porous film and a multilayer porousfilm, drying temperature, winding tension and the like are preferred tobe appropriately controlled.

[Separator]

Separator of the present embodiment has a thermoplastic polymer on atleast a part of at least one of the surfaces of a polyolefin microporousfilm.

(Peel Strength)

To the outermost surface of the separator for the electricity storagedevice having a thermoplastic polymer coating layer, an aluminum foil(e.g., positive electrode collector) is pressed at a temperature of 25°C. and a pressure of 5 MPa for 3 minutes and peeled. At this time, thepeel strength (hereinafter referred to also as “normal temperature peelstrength”) is preferably 8 gf/cm or less and more preferably 7 gf/cm orless and further preferably 6 gf/cm or less. If the peel strength is 8gf/cm or less, stickiness is further suppressed and excellent slitperformance and winding properties of the separator tend to be obtained.

The present inventors further surprisingly found that if the peelstrength falls within the above range, adhesiveness of the separator ofthe present embodiment to electrodes by hot-press is improved.

The reason why such an effect can be obtained is not known; however, itis considered that the normal temperature peel strength within the aboverange indicates that a large amount of thermoplastic resin having a highglass-transition temperature is present on the side of the outermostsurface of the separator of the present embodiment; whereas a largeamount of thermoplastic resin having a low glass-transition temperatureis present on the side of the separator of the present embodiment facinga polyolefin microporous film.

In other words, since a large amount of thermoplastic resin having ahigh glass-transition temperature is present on the side of theoutermost surface of the separator of the present embodiment, stickinessis suppressed. In addition, a thermoplastic resin having a highglass-transition temperature is excellent in adhesiveness to anelectrode, with the result that the separator having low stickiness andexcellent adhesiveness to electrodes was conceivably obtained.

Since a large amount of thermoplastic resin having a lowglass-transition temperature is present on the side of the separator ofthe present embodiment facing a polyolefin microporous film,adhesiveness between the polyolefin microporous film serving as asubstrate and the thermoplastic resin improves. As a result, peeling atthe interface between the polyolefin microporous film and thethermoplastic resin is suppressed and a separator excellent inadhesiveness to an electrode was conceivably obtained.

To the outermost surface of the separator for the electricity storagedevice having a thermoplastic polymer coating layer, an aluminum foil(e.g., positive electrode collector) is pressed at a temperature of 80°C. and a pressure of 10 MPa for 3 minutes and peeled. At this time, thepeel strength (hereinafter referred to also as “heat-peel strength”) ispreferably 10 gf/cm or more and more preferably 15 gf/cm or more andfurther preferably 20 gf/cm or more. Note that the heat-peel strengthcan be measured by a method described in Examples.

The separator having a heat-peel strength falling within the above rangeis preferably applied to an electricity storage device (described later)since adhesiveness between electrodes and the separator is excellent.

When a separator and a negative electrode are laminated in the presenceof an electrolytic solution, pressurized at a pressure of 10 MPa and atemperature of 80° C. for 2 minutes and then the separator and thenegative electrode are peeled, an active material preferably remains(adhering) on the separator in an area ratio of 10% or more.

The 90° peel strength between a polyolefin microporous film and athermoplastic polymer coating layer is preferably 6 gf/mm or more, morepreferably 7 gf/mm or more and more preferably 8 gf/mm or more. If the90° peel strength between a polyolefin microporous film and athermoplastic polymer coating layer is 6 gf/mm or more, more excellentadhesiveness between the thermoplastic polymer and the polyolefinmicroporous film tends to be obtained. As a result, the falling-off ofthe thermoplastic polymer layer is suppressed and excellent adhesivenessbetween the separator and electrodes tends to be obtained.

The film thickness of a separator for an electricity storage device ispreferably 2 μm or more, more preferably 5 μm or more. The upper limitthereof is preferably 100 μm or less, more preferably 50 μm or less andfurther preferably 30 μm or less. A film thickness of 2 μm or more ispreferred since the strength of a separator for an electricity storagedevice is secured. In contrast, a film thickness of 100 μm or less ispreferred since satisfactory charge-discharge characteristics areobtained.

In the present embodiment, the air permeability of a separator for anelectricity storage device is preferably 10 sec/100 cc or more and morepreferably 50 sec/100 cc or more. The upper limit thereof is preferably10000 sec/100 cc or less and further preferably 1000 sec/100 cc or less.An air permeability of 10 sec/100 cc or more is preferred since, if theseparator is employed as a separator for an electricity storage device,self-discharge of the electricity storage device can be furthersuppressed. In contrast, an air permeability of 10000 sec/100 cc or lessis preferred since satisfactory charge-discharge characteristics can beobtained. The air permeability of a separator for an electricity storagedevice can be controlled by varying the stretching temperature andstretching ratio in producing the polyolefin microporous film, the arearatio of a thermoplastic polymer and existence form thereof.

A short-circuit temperature, which is used as an index for heatresistance of a separator for an electricity storage device, ispreferably 140° C. or more, more preferably 150° C. or more and furtherpreferably 160° C. or more. A short-circuit temperature of 160° C. ormore is preferred in view of safety of an electricity storage device ifthe separator is used as a separator for the electricity storage device.

(Method for Producing Separator for an Electricity Storage Device)

A method for forming a thermoplastic polymer on a polyolefin microporousfilm is not particularly limited. For example, a method of applying athermoplastic polymer-containing coating liquid to a polyolefinmicroporous film is mentioned.

The method of applying a thermoplastic polymer-containing coating liquidto a porous film is not particularly limited as long as a requisitelayer-thickness and coating area can be realized. Examples of the methodinclude a gravure coater method, a small-diameter gravure coater method,a reverse roll coater method, a transfer roll coater method, a kisscoater method, a dip coater method, a knife coater method, an air doctorcoater method, a blade coater method, a rod coater method, a squeezecoater method, a cast coater method, a die-coater method, a screenprinting method, a spray coating method, spray coater coating method andan ink jet coating method. Among these, a gravure coater method or aspray coating method is preferred since the degree of freedom of theshape of a thermoplastic polymer after coating is high and a preferablearea ratio can be easily obtained.

When a thermoplastic polymer is applied to a polyolefin microporousfilm, if a coating liquid enters the interior of the microporous film,the surface and interior of pores are buried with an adhesive resin andpermeability reduces. For this reason, as a medium for the coatingliquid, a poor solvent for a thermoplastic polymer is preferred. A poorsolvent for a thermoplastic polymer is preferably used as a medium forthe coating liquid. This is because, if so, the coating liquid does notenter the interior of the microporous film and an adhesive polymer isprimarily present on the surface of the microporous film, with theresult that reduction in permeability is suppressed. As such a medium,water is preferable. A medium which can be used in combination withwater, which is not particularly limited, may be e.g., ethanol andmethanol.

A surface treatment is preferably applied to a porous film surface priorto application of a coating liquid. This is because, if so, the coatingliquid can be easily applied; at the same time, adhesiveness between theporous layer and an adhesive polymer is improved. A surface treatmentmethod is not particularly limited to as long as the method does notsignificantly damage the porous structure of the porous film. Examplesof the method include a corona discharge treatment method, a plasmatreatment method, a mechanical rough-surface treatment method, a solventtreatment method, an acid treatment method and an ultraviolet oxidationmethod.

A method for removing a solvent from the coating film after coating isnot particularly limited as long as a porous film is not negativelyaffected. Examples of the method include a method of drying a porousfilm at its melting point or less while immobilizing the porous film, amethod of drying the film at low temperature under reduced pressure anda method of soaking the coating film in a poor solvent for an adhesivepolymer to solidify the adhesive polymer; at the same time, extractingthe solvent.

The separator for the electricity storage device is excellent inhandling performance at the time of rolling and provides excellent ratecharacteristics to the electricity storage device, and further hasexcellent adhesiveness between a thermoplastic polymer and a polyolefinmicroporous film and excellent permeability. For this reason, use of theseparator for the electricity storage device is not particularly limitedto; and, the separator is suitably used, for example, in batteries suchas a non-aqueous electrolyte secondary battery, condensers, separatorsfor electricity storage devices such as capacitors, and separation ofsubstances.

[Laminate]

The laminate according to the present embodiment is formed by laminatinga separator as mentioned above and electrodes. The separator of thepresent embodiment is allowed to adhere to electrodes and can be used asa laminate. The “adhesion” herein means that the heat-peel strength asmentioned above between a separator and an electrode is preferably 10gf/cm or more, more preferably 15 gf/cm or more and further preferably20 gf/cm or more.

The laminate is excellent in handling performance at the time of rollingand provides excellent rate characteristics to the electricity storagedevice and further has excellent adhesiveness between a thermoplasticpolymer and a polyolefin microporous film and excellent permeability.For this reason, use of the laminate is not particularly limited to;and, the laminate can be suitably used, for example, in batteries suchas a non-aqueous electrolyte secondary battery, condensers andelectricity storage devices such as capacitors.

As the electrode to be used in the laminate of the present embodiment,those described later in Section of “electricity storage device” can beused.

A method for producing a laminate by using the separator of the presentembodiment is not particularly limited to. The laminate can be produced,for example, by laminating the separator of the present embodiment andelectrodes and, if necessary, applying heat and/or pressure. Heat and/orpressure can be applied in laminating electrodes and a separator.Alternatively, the laminate can be produced by applying heat and/orpressure to a wound body, which is obtained by laminating electrodes anda separator and then rolling in a circular or flat spiral form.

Alternatively, the laminate can be produced by obtaining a laminate ofpositive electrode-separator-negative electrode-separator, or negativeelectrode-separator-positive electrode-separator stacked in the orderlike a flat plate, and if necessary applying heat and/or pressure.

More specifically, the laminate can be produced by preparing theseparator of the present embodiment so as to have a longitudinal shapehaving a width of 10 to 500 mm (preferably 80 to 500 mm) and a length of200 to 4000 m (preferably 1000 to 4000 m) and laminating the separatorso as to satisfy the order of positive electrode-separator-negativeelectrode-separator, or negative electrode-separator-positiveelectrode-separator, and if necessary applying heat and/or pressure.

The temperature of heat is preferably 40 to 120° C. The heating time ispreferably 5 seconds to 30 minutes. The pressure is preferably 1 to 30MPa. The time for applying a pressure is preferably 5 seconds to 30minutes. As the order of application of heat and pressure, heat isapplied and then pressure is applied or pressure is applied and thenheat is applied, or pressure and heat may be simultaneously applied. Ofthem, simultaneous application of pressure and heat is preferable.

[Electricity Storage Device]

The separator of the present embodiment can be used in batteriescondensers, separators in capacitors or the like and separation ofsubstances. The separator, particularly if it is used as a separator fora non-aqueous electrolyte battery, can provide adhesiveness toelectrodes and excellent battery performance.

Now, preferred aspects of the case where the electricity storage deviceis a non-aqueous electrolyte secondary battery will be described below.

In the case where a non-aqueous electrolyte secondary battery isproduced using the separator of the present embodiment, a positiveelectrode, a negative electrode and a non-aqueous electrolyte are notlimited to and those known in the art can be used.

Examples of the positive electrode material include, but notparticularly limited to, lithium-containing composite oxides such asLiCoO₂, LiNiO₂, spinel type LiMnO₄ and olivine type LiFePO₄.

Examples of the negative electrode material include, but notparticularly limited to, carbon materials such as graphite, acarbonaceous material rarely graphitized, a carbonaceous material easilygraphitized and a carbon composite material; silicon, tin, metalliclithium and various types of alloy materials.

The non-aqueous electrolyte is not particularly limited to; and, anelectrolytic solution prepared by dissolving an electrolyte in anorganic solvent can be used. Examples of the organic solvent includepropylene carbonate, ethylene carbonate, dimethyl carbonate, diethylcarbonate and ethyl methyl carbonate. Examples of the electrolyteinclude lithium salts such as LiClO₄, LiBF₄ and LiPF₆.

A method for producing an electricity storage device using the separatorof the present embodiment is not particularly limited. In the case wherethe electricity storage device is a secondary battery, the electricitystorage device can be produced, for example, by preparing the separatorof the present embodiment so as to have a longitudinal shape having awidth of 10 to 500 mm (preferably 80 to 500 mm) and a length of 200 to4000 m (preferably 1000 to 4000 m); laminating the separator so as tosatisfy the order of positive electrode-separator-negativeelectrode-separator, or negative electrode-separator-positiveelectrode-separator; rolling the laminate into circular or flat spiralform to obtain a wound body; housing the wound body in a battery can andfurther injecting an electrolytic solution in the battery can. At thistime, heat and/or pressure may be applied to the wound body to form theaforementioned laminate. Alternatively, the electricity storage devicecan be produced by using a wound body obtained by rolling theaforementioned laminate into a circular or flat spiral form.Alternatively, the electricity storage device can be produced via a stepof covering a flat laminate formed in the order of positiveelectrode-separator-negative electrode-separator, or negativeelectrode-separator-positive electrode-separator or the aforementionedlaminate with a bag-like film, and injecting an electrolytic solution,and as necessary, a step of applying heat and/or pressure to the bag.The above step of applying heat and/or pressure can be carried outbefore and/or after the step of injecting the electrolytic solution.

Note that the aforementioned measurement values of various parametersare values measured in accordance with measurement methods laterdescribed in Examples, unless otherwise specified.

Second Embodiment

The porous film according to the present embodiment has

a polyolefin microporous film and a thermoplastic polymer coating layercovering at least a part of at least one of the surfaces of thepolyolefin microporous film, in which

the thermoplastic polymer coating layer contains a thermoplastic polymerhaving a glass-transition temperature of −10° C. or more and 40° C. orless, and

a degree of swelling with an electrolytic solution of 5 times or less.

In the second embodiment, matters except those described below are thesame as those of the first embodiment.

(Glass-Transition Temperature)

In the present embodiment, the glass-transition temperature of athermoplastic polymer is preferably −10° C. or more and 40° C. or less,more preferably 0° C. or more and 35° C. or less and further preferably15° C. or more and 30° C. or less. In the present embodiment, theglass-transition temperature of a thermoplastic polymer is specified as−10° C. or more and 40° C. or less. Owing to this, adhesiveness betweenmutual thermoplastic polymers or between the thermoplastic polymer andthe polyolefin microporous film is effectively suppressed. In contrast,adhesiveness between a thermoplastic polymer and a polyolefinmicroporous film tends to be further improved.

Note that the thermoplastic polymer may have a plurality ofglass-transition temperatures. In this case, at least one of theglass-transition temperatures may be present in the above temperaturerange. Preferably, all glass-transition temperatures are present in theabove temperature range.

In the present embodiment, the average thickness of a thermoplasticpolymer coating layer is not particularly limited. The average thicknessof a thermoplastic polymer coating layer on one of the surfaces ispreferably 1.5 μm or less, more preferably 1.0 μm or less and furtherpreferably 0.5 μm or less. The average thickness of a thermoplasticpolymer is preferably 1.5 μm or less. This is because, if so, reductionin permeability caused by the thermoplastic polymer and adhesivenessbetween mutual thermoplastic polymers or between the thermoplasticpolymer and the polyolefin microporous film are effectively suppressed.

The average thickness of a thermoplastic polymer can be controlled byvarying the polymer concentration of a coating liquid, amount of polymersolution to be applied, coating method and coating conditions.

The thickness of a thermoplastic polymer coating layer can be measuredby a method described in Examples.

The separator of the present embodiment has a thermoplastic polymer atleast on a part of at least one of the surfaces of a polyolefinmicroporous film. The area ratio (%) of the polyolefin microporous filmcovered with the thermoplastic polymer coating layer is preferably 70%or less, more preferably 50% or less, further preferably 45% or less andstill further preferably 40% or less based on 100% of the total area ofthe polyolefin microporous film. Furthermore, the area ratio (%) ispreferably 5% or more. If the area ratio is 70% or less, blockage of thepores of the polyolefin microporous film by the thermoplastic polymer issuppressed and permeability tends to be successfully further improved.In contrast, if the area ratio is 5% or more, adhesiveness tends to bemore improved. The area ratio herein is calculated by a method laterdescribed in Examples.

The area ratio can be controlled by varying the polymer concentration ofa coating liquid, amount of polymer solution to be applied, coatingmethod and coating conditions.

In the present embodiment, the gel fraction of a thermoplastic polymer,which is not particularly limited, is preferably 90% or more and morepreferably 95% or more. If the gel fraction of a thermoplastic polymeris 90% or more, dissolution of the thermoplastic polymer in anelectrolytic solution is suppressed and strength of the thermoplasticpolymer within a battery tends to be more improved. The gel fractionherein can be obtained based on the measurement of toluene-insolublematter as described later in Examples.

The gel fraction can be controlled by varying the types and ratio ofmonomers to be polymerized and polymerization conditions.

The thermoplastic polymer coating layer, on the polyolefin microporousfilm, has a portion containing the thermoplastic polymer and a portionnot containing the thermoplastic polymer in a sea-island configuration;preferably, the portion containing the thermoplastic polymer is formedin a dot pattern. Examples of the shape of islands in sea, which is notparticularly limited to, include a linear, dot, grid, stripe andhexagonal patterns. Of them, in view of securing permeability anduniform adhesiveness to electrodes, dots are more preferable. Dotsindicate that a portion containing a thermoplastic polymer and a portionnot containing the thermoplastic polymer are in a sea-islandconfiguration on the polyolefin microporous film. The interval of dotsis preferably 5 μm to 500 μm in view of both adhesiveness to electrodesand cycle characteristics. The average major axis of dots is preferably20 μm or more and 1000 μm or less, more preferably 20 μm or more and 800μm or less and further preferably 50 μm or more and 500 μm or less.

In the present embodiment, adhesiveness of the porous film to theelectrode active material measured by a method described later ispreferably 30% or more.

(Use of Porous Film, Etc.)

Use of the porous film according to the present embodiment is notparticularly limited to. The porous film is excellent in handlingperformance at the time of rolling. When the porous film is used as aseparator for an electricity storage device, the electricity storagedevice shows excellent rate characteristics. Furthermore, adhesivenessbetween a thermoplastic polymer and a polyolefin microporous film andpermeability are excellent. For these reasons, the porous film can besuitably used, for example, in batteries such as a non-aqueouselectrolyte secondary battery, condensers, separators for electricitystorage devices such as capacitors and separation of substances.

Examples

Now, the present invention will be more specifically described based onExamples and Comparative Examples below; however, the present inventionis not limited to Examples. Measurement and evaluation methods forvarious physical properties employed in the following ProductionExamples, Examples and Comparative Examples are as follows. Note thatmeasurement and evaluation were carried out in the conditions of roomtemperature (23° C.) 1 atm and a relative humidity of 50%, unlessotherwise specified.

[Measurement Method] (1) Viscosity Average Molecular Weight (HereinafterReferred to Also as “Mv”)

Limiting viscosity [η] in a decalin solvent at 135° C. was obtainedbased on ASRM-D4020 and Mv of polyethylene was calculated in accordancewith the following formula:

[η]=0.00068×Mv ^(0.67)

Furthermore, Mv of polypropylene was calculated in accordance with thefollowing formula:

[η]=1.10×Mv ^(0.80)

(2) Weight Per Unit Area of Polyolefin Microporous Film

A sample of 10 cm×10 cm square was excised out from a polyolefinmicroporous film and weight of the sample was measured by electronicbalance AEL-200 manufactured by Shimadzu Corporation. The obtainedweight was multiplied with 100 to calculate the weight per unit area perfilm (m²) (g/m²)

(3) Porosity (%) of Polyolefin Microporous Film

A sample of 10 cm×10 cm square was excised out from a polyolefinmicroporous film and the volume (cm³) and mass (g) of the sample wereobtained. Provided that the film density was 0.95 (g/cm³), the porositywas calculated in accordance with the following formula:

Porosity=(volume−mass/film density)/volume×100

(4) Air Permeability (Sec/100 cc)

Degree of air infiltration resistance, which was measured in accordancewith JISP-8117 by Gallery air permeability measurement system G-B2(trade mark) manufactured by TOYOSEIKI KOGYO CO. LTD., was specified asair permeability.

(5) Puncture Strength (g) of Polyolefin Microporous Film

Using a handy compression tester KES-G5 (trade mark) manufactured byKATO TECH CO., LTD., a polyolefin microporous film was immobilized by asample holder having an opening portion of 11.3 mm in diameter.Subsequently, the center portion of the polyolefin microporous filmimmobilized was subjected to a puncture test using a needle having a topcurvature radius of 0.5 mm at a puncturing rate of 2 mm/sec under anatmosphere of 25° C. A maximum puncturing load was specified as thepuncture strength (g).

(6) Average Pore Diameter (μm)

It is known that the fluid in a capillary flows in accordance with theKnudsen flow when the mean free path of the fluid is larger than thepore diameter of the capillary, whereas the fluid flows in accordancewith the Poiseuille flow when the mean free path of the fluid is smallerthan the pore diameter of the capillary. Then, it is assumed that theair flow in measuring air permeability of a microporous film follows inaccordance with the Knudsen flow; whereas the water flow in measuringwater penetration rate of a microporous film follows in accordance withthe Poiseuille flow.

The average pore diameter d (μm) was obtained based on air permeabilityrate constant R_(gas) (m³/(m²·sec·Pa)), water permeability rate constantR_(liq) (m³/(m²··Pa)), air molecular speed ν (m/sec), water viscosity η(Pa·), standard pressure P_(s) (=101325 Pa), porosity ε (%) and filmthickness L (μm) in accordance with the following formula:

d=2ν×(R _(liq) /R _(gas))×(16η/3Ps)×10⁶

R_(gas) can be obtained based on air permeability (sec) in accordancewith the following formula:

R _(gas)=0.0001/(air permeability×(6.424×10⁻⁴)×(0.01276×101325))

R_(liq) can be obtained based on a water penetration rate(cm³/(cm²··Pa)) in accordance with the following formula:

R _(liq)=water penetration rate/100

Note that water penetration rate can be obtained as follows. Amicroporous film soaked in ethanol in advance was set in a cell made ofstainless steel and having a diameter of 41 mm. After the film waswashed with water to remove ethanol, water was allowed to permeate at adifferential pressure of about 50000 Pa. After 120 sec, the volume ofwater (cm³) permeated was measured. Based on this, a permeable watervolume per unit time/unit pressure/unit area was calculated andspecified as a water penetration rate.

The value ν was obtained in accordance with the following formula basedon gas constant R (=8.314), absolute temperature T (K), circularconstant π, and average molecular weight M of air (=2.896×10⁻² kg/mol).

ν=((8R×T)/(π×M))^(1/2)

(7) Thickness (μm) (7)-1 Film Thickness (μm) of Polyolefin MicroporousFilm and a Separator for an Electricity Storage Device

A sample of 10 cm×10 cm square was excised out from each of a polyolefinmicroporous film and a separator for an electricity storage device. Ninesites (3 points×3 points) in the form of a lattice were selected andmeasured for film thickness by a micro thickness gage (type KBMmanufactured by TOYO SEIKI SEISAKU-SHO, LTD.) at room temperature of23±2° C. The averages of 9 point measurement values of individual filmswere specified as the film thickness (μm) of the polyolefin microporousfilm and the film thickness (μm) of the separator for the electricitystorage device, respectively.

(7)-2 Thickness of a Thermoplastic Polymer Coating Layer (μm)

The thickness of a thermoplastic polymer coating layer was measured byobserving a section of a separator under a scanning electron microscope(SEM) “model S-4800, manufactured by HITACHI Ltd.” A sample of about 1.5mm×2.0 mm was excised out from the separator and stained with ruthenium.The sample stained and ethanol were placed in a gelatin capsule andfrozen with liquid nitrogen and then the sample was broken by a hammer.Osmium was vapor-deposited on the sample and observed at an accelerationvoltage of 1.0 kV at a magnification of 30000× to determine thethickness of the thermoplastic polymer layer. Note that in an SEM imageof the section, the outermost surface region where a porous structure ofa polyolefin microporous film was not observed was determined as theregion of a thermoplastic polymer coating layer.

(8) Glass-Transition Temperature of Thermoplastic Polymer

An appropriate amount of coating liquid (nonvolatile content=38 to 42%,pH=9.0) of a thermoplastic polymer was taken on an aluminum plate anddried by a hot-air dryer at 130° C. for 30 minutes. After dried, analuminum measurement container was charged with the dried film (about 17mg) and a DSC curve and a DDSC curve were obtained by a DSCdetermination apparatus (DSC6220, manufactured by Shimadzu Corporation)under a nitrogen atmosphere. Note that measurement conditions were asfollows:

(First-Step Temperature Raising Program)

Temperature was raised from 70° C. at a rate of 15° C. per minute. Afterthe temperature reaches 110° C., the temperature was maintained for 5minutes.

(Second-Step Temperature Decreasing Program)

Temperature was allowed to decrease from 110° C. at a rate of 40° C. perminute. After the temperature reaches −50° C., the temperature wasmaintained for 5 minutes.

(Third-Step Temperature Raising Program)

Temperature was raised from −50° C. at a rate of 15° C. per minute up to130° C. During the third-step temperature raising time, DSC and DDSCdata were obtained.

The intersection of the base line (the base line of the DSC curveobtained linearly extended toward a high temperature side) with atangent line at an inflection point (point at which a convex curve waschanged to a concave curve) was specified as a glass-transitiontemperature (Tg).

(9) Gel Fraction of Thermoplastic Polymer (Toluene-Insoluble Matter)

On a Teflon (registered trade mark) plate, a thermoplastic polymercoating liquid (nonvolatile content=38 to 42%, pH=9.0) was placeddropwise by a dropper (5 mm or less in diameter) and dried by a hot-airdryer at 130° C. for 30 minutes. After dried, about 0.5 g (a) of thedried film was weighed and placed in a 50 mL-polyethylene container. Tothe container, toluene (30 mL) was poured. The container was shaken for3 hours at room temperature. Thereafter, the content was filtered by a325 mesh. The toluene-insoluble matter remaining on the mesh was driedby a hot-air dryer at 130° C. for one hour together with the mesh. Notethat the dry weight of the 325 mesh used herein was previously measured.

After toluene was evaporated, the dry weight (b) of toluene-insolublematter was obtained by subtracting the weight of the 325 mesh previouslymeasured from the weight of the dried toluene-insoluble matter+the 325mesh. The gel fraction (toluene-insoluble matter) was calculated inaccordance with the following calculation formula:

Gel fraction (toluene-insoluble matter) of thermoplasticpolymer=(b)/(a)×100[%]

(10) Degree of Swelling (Times) of a Thermoplastic Polymer with anElectrolytic Solution

A thermoplastic polymer or a solution in which a thermoplastic polymerwas dispersed was allowed to stand still in an oven at 130° C. for onehour. 0.5 g of the dried thermoplastic polymer was then excised out andplaced in a 50 mL-vial container together with 10 g of a solvent mixtureof ethylene carbonate:ethyl methyl carbonate=1:2 (volume ratio) toimpregnate the polymer with the solvent for 3 hours. Thereafter, thesample was taken out, washed with the aforementioned solvent mixture andthe weight (Wa) of the sample was measured. Thereafter, the sample wasallowed to stand still in an oven at 150° C. for one hour and the weight(Wb) of the sample was measured. The degree of swelling of athermoplastic polymer with an electrolytic solution was measured inaccordance with the following formula:

Degree of swelling (times) of a thermoplastic polymer with anelectrolytic solution=(Wa−Wb)(Wb)

(11) Area Ratio of Polyolefin Microporous Film Covered withThermoplastic Polymer Coating Layer

The area ratio of a polyolefin microporous film covered with athermoplastic polymer coating layer was determined by a scanningelectron microscope (SEM), “model S-4800, manufactured by HITACHI, Ltd.”Osmium was vapor-deposited on a separator for an electricity storagedevice and the separator was observed at an acceleration voltage of 1.0kV and a magnification of 50× to obtain the area. Using the obtainedarea, the area ratio was calculated in accordance with the followingformula. Note that the region in which the surface of a polyolefinmicroporous film was not seen in the SEM image was specified as athermoplastic polymer region. The measurement was repeated three timesand an average value thereof was specified as the area ratio of thesample.

The area ratio of a thermoplastic polymer (%)=the area of thermoplasticpolymer the total area of image×100

(12) Existence Form (Coated Form) of Thermoplastic Polymer Coating Layer

Existence form (coated form) of a thermoplastic polymer coating layerwas determined by vapor-depositing osmium onto a separator for anelectricity storage device and observing the separator by a scanningelectron microscope (SEM) “model S-4800, manufactured by HITACHI, Ltd.”at an acceleration voltage of 1.0 kV and a magnification of 50×. Notethat the state in which most of the polyolefin microporous film werecovered with the thermoplastic polymer (including a part of thethermoplastic polymer, for example, aggregated and failed to completelycover the polyolefin) was specified as “non-dot form”.

(13-1) Area Ratio of Particulate Thermoplastic Polymer

The area ratio (S) of a particulate thermoplastic polymer based on thethermoplastic polymer present on the outermost surface of a separatorfor an electricity storage device was calculated in accordance with thefollowing formula:

S (%)=Area of particulate thermoplastic polymer÷total area ofthermoplastic polymer present on the outermost surface of separator×100

The area of a particulate thermoplastic polymer was determined by use ofa scanning electron microscope (SEM) “model S-4800, manufactured byHITACHI, Ltd.” More specifically, osmium was vapor-deposited onto aseparator for an electricity storage device and observed at anacceleration voltage of 1.0 kV and a magnification of 30000×.

(13-2) Average Particle Size (μm) of Particulate Thermoplastic Polymer

The average particle size of a particulate thermoplastic polymer wasdetermined by vapor-depositing osmium onto a separator for anelectricity storage device and observing the separator by a scanningelectron microscope (SEM) “model S-4800, manufactured by HITACHI, Ltd.”at an acceleration voltage of 1.0 kV and a magnification of 30000×. Thelargest diameter of the particulate thermoplastic polymer was specifiedas a particle size and the particle sizes of 20 particles were averagedto obtain an average particle size.

(14) Average Major Axis (μm) of Dot-Form Thermoplastic Polymer

Average major axis of dot-form thermoplastic polymer was determined byvapor-depositing osmium onto a separator for an electricity storagedevice and observing the separator by a scanning electron microscope(SEM) “model S-4800, manufactured by HITACHI, Ltd.” at an accelerationvoltage of 1.0 kV and a magnification of 50×. In the portion where thethermoplastic polymer was present, if a thermoplastic polymer waspresent in the form of dots, the largest diameter of a dot was specifiedas a major axis and the major axes of 20 dots were averaged to obtain anaverage major axis of dots. If a thermoplastic polymer was present inthe form of lines, grids, stripes and hexagonal patterns, the widestline width of the form was specified as the major axis and the majoraxes of 20 forms were averaged to obtain an average major axis.

(15) Average Particle Size of Thermoplastic Polymer

The average particle size of a thermoplastic polymer was determined by aparticle-size measurement apparatus (Microtrac UPA150, manufactured byNikkiso Co., Ltd.). Particle sizes were measured in the followingconditions: loading index=0.15 to 0.3, measurement time: 300 seconds.Based on the obtained data, 50% particle size was obtained and describedas a particle size.

[Evaluation Method] (16) Adhesiveness Between Separator and Electrode

The adhesiveness between a separator and an electrode was evaluated bythe following procedure.

(Fabrication of Positive Electrode)

Lithium cobalt composite oxide (LiCoO₂) (92.2 mass %) as a positiveelectrode active material, a scale-like graphite and acetylene black(2.3 mass % for each) as an electrical conducting material andpolyvinylidene fluoride (PVDF) (3.2 mass %) as a binder were dispersedin N-methylpyrrolidone (NMP) to prepare a slurry. The slurry was appliedto one of the surfaces of aluminum foil serving as a positive electrodecollector of 20 μm in thickness by a die coater, dried at 130° C. for 3minutes and thereafter subjected to compression molding by a rollpressing machine. The application herein was made such that the amountof positive electrode active material coated was 250 g/m² and the bulkdensity of the active material was 3.00 g/cm³.

(Fabrication of Negative Electrode)

An artificial graphite (96.9 mass %) as a negative-electrode activematerial, an ammonium salt of carboxymethylcellulose (1.4 mass %) as abinder and styrene-butadiene copolymer latex (1.7 mass %) were dispersedin purified water to prepare a slurry. The slurry was applied to one ofthe surfaces of copper foil serving as a negative electrode collector of12 μm in thickness by a die coater, dried at 120° C. for 3 minutes andthereafter subjected to compression molding by a roll pressing machine.The application herein was made such that the amount of negativeelectrode active material coated was 106 g/m² and the bulk density ofthe active material was 1.35 g/cm³.

(Adhesiveness Test)

The negative electrode obtained by the above method was cut into piecesof 20 mm in width and 40 mm in length. On each of the negative electrodepieces, an electrolytic solution (manufactured by TOMIYAMA PURE CHEMICALINDUSTRIES, Ltd.), which was obtained by mixing ethylene carbonate anddiethyl carbonate in a ratio of 2:3 (volume ratio), was dripped so as tosoak the negative electrode piece and a separator was superposed on thepiece. The laminate obtained was placed in an aluminum zip and pressedin the conditions of 80° C. and 10 MPa for 2 minutes. Thereafter, thelaminate was taken out and the separator was removed from the electrode.

(Evaluation Criteria)

◯: a negative-electrode active material remained (adhering) in 30% ormore of area of a separator.

Δ: a negative-electrode active material remained (adhering) in 10% ormore and less than 30% of area of a separator.

x: a negative-electrode active material remained (adhering) in less than10% of area of a separator.

(17-1) Heat-Peel Strength and Stickiness (Peel Strength of Separator)

A separator and a positive electrode collector (aluminum foil, 20 μm,manufactured by Fuji Imprex Corp.) as a substrate to be attached werecut into pieces of 30 mm×150 mm and laminated. Thereafter, each of theresultant laminates was sandwiched by Teflon (registered trade mark)sheet (NAFLON PTFE sheet TOMBO-No. 9000, manufactured by NICHIASCorporation). The laminates were pressed in the following conditions toobtain test samples.

Condition 1) pressed at a temperature of 25° C. and a pressure of 5 MPafor 3 minutes

Condition 2) pressed at a temperature of 40° C. and a pressure of 5 MPafor 3 minutes

Condition 3) pressed at a temperature of 80° C. and a pressure of 10 MPafor 3 minutes

The peel strength of the test samples obtained was measured by use ofautograph AG-IS (trade mark), manufactured by Shimadzu Corporation, inaccordance with JISK6854-2 at a tension rate of 200 mm/minute. Based onthe obtained results, the peel strength of the separator was evaluatedin accordance with the following evaluation criteria.

Evaluation Criteria for Stickiness (Handling Performance of Separator):Evaluation Criteria for Peel Strength after Pressed in Condition 1)

⊚: peel strength was 4 gf/cm or less

◯: peel strength was more than 4 gf/cm and 6 gf/cm or less

Δ: peel strength was more than 6 gf/cm and 8 gf/cm or less

x: peel strength was more than 8 gf/cm

Evaluation Criteria for Stickiness (Handling Performance of Separator):Evaluation Criteria for Peel Strength after Pressed in Condition 2)

⊚: peel strength was 4 gf/cm or less

◯: peel strength was more than 4 gf/cm and 6 gf/cm or less

Δ: peel strength was more than 6 gf/cm and 8 gf/cm or less

x: peel strength was more than 8 gf/cm

Evaluation Criteria for Heat-Peel Strength: Evaluation Criteria for PeelStrength after Pressed in Condition 3)

◯: peel strength was 10 gf/cm or more

x: peel strength was less than 10 gf/cm

(17-2) Handling Performance

From a porous film, two pieces (2 cm in width×15 cm in length) were cutout, arranged such that thermoplastic polymer coating surfaces facedeach other and pressed at 25° C. and 5 MPa for 3 minutes. An edge of thesample obtained was picked up and folded back at an angle of 180° andpeeled at a distance of 25 mm. Then, in accordance with JISZ7127, theedges of each of the porous films were immobilized by a chuck of atension tester (AG-100A manufactured by Shimadzu Corporation) and peeledat a rate of 5.0 mm/s at an angle of 180° to measure adhesion force.Values of load applied to the sample in order to peel the film from 25mm until 75 mm after initiation of measurement were averaged andspecified as the peel strength of the porous film. Based on the obtainedresults, handling performance was evaluated in the following evaluationcriteria.

◯: peel strength was less than 4 gf

Δ: 4 gf or more and less than 8 gf

x: 8 gf or more

(18) Wettability of Thermoplastic Polymer

A thermoplastic polymer solution (solid substance concentration: 3%) wasapplied onto an A4 size polyolefin microporous film in accordance with agravure method using a bar coater, dried in an oven of 60° C. for 5minutes to remove water. After dried, a 10 cm-square piece was excisedout from the separator, soaked in ethanol in a petri dish and washeddirectly by an ultrasonic cleaner (model US-102, manufactured by SNDCo., Ltd., oscillatory frequency: 38 kHz) for one minute. The separatorpiece was taken out and dried by evaporating ethanol at normaltemperature.

(Evaluation Criteria)

◯: polyolefin microporous film on the surface of which a thermoplasticpolymer was present.

x: polyolefin microporous film on the surface of which a thermoplasticpolymer was not present.

(19-1) Adhesion Force Between Thermoplastic Polymer Coating Layer andPolyolefin Microporous Film

To the thermoplastic polymer coating layer of a separator, a tape of 12mm in width×100 mm in length (manufactured by 3M) was attached. Theforce applied when the tape was removed from the sample at a rate of 50mm/minute was measured by 90°-peel strength measurement apparatus(product name IP-5N, manufactured by IMADA CO., LTD.). Based on themeasurement results obtained, the adhesion force was evaluated inaccordance with the following evaluation criteria.

◯: 6 gf/mm or more

x: less than 6 gf/mm

(19-2) Adhesiveness Between Thermoplastic Polymer and PolyolefinMicroporous Film

A thermoplastic polymer solution (solid substance concentration: 3%) wasapplied onto an A4 size polyolefin microporous film in accordance with agravure method using a bar coater and dried in an oven of 60° C. for 5minutes to remove water, to obtain a porous film. After dried, a 10cm-square piece was excised out from the porous film obtained, soaked inethanol in a petri dish and washed directly by an ultrasonic cleaner(model US-102, manufactured by SND Co., Ltd., oscillatory frequency: 38kHz) for 5 minutes. The porous-film piece was taken out and dried byevaporating ethanol at normal temperature. The obtained porous-filmpiece was observed with the naked eye. Based on the observation resultsobtained, the adhesiveness between the thermoplastic polymer and thepolyolefin microporous film was evaluated in accordance with thefollowing evaluation criteria.

◯: polyolefin microporous film on the surface of which a thermoplasticpolymer was present

x: polyolefin microporous film on the surface of which a thermoplasticpolymer was not present or even in the case of a polyolefin microporousfilm on the surface of which a thermoplastic polymer was present, thethermoplastic polymer slips off when the portion of the thermoplasticpolymer was touched by a finger.

(20) Winding properties and cycle characteristics of battery

(20-1) Preparation of Sample for Evaluation <Electrode>

A positive electrode and a negative electrode were fabricated in thesame manner as in Section (16) adhesiveness between separator andelectrode. The positive electrode and negative electrode were cut toobtain bands having a width of about 57 mm and 58 mm, respectively, toprovide electrodes for evaluation.

<Preparation of Non-Aqueous Electrolyte>

A non-aqueous electrolyte was prepared by dissolving LiPF₆ as a solutein a solvent mixture of ethylene carbonate/ethyl methyl carbonate=1/2(volume ratio) so as to obtain a concentration of 1.0 mol/L.

<Separator>

The separator obtained in each of Examples and Comparative Examples wassliced to obtain a 60 mm-separator band for evaluation.

(20-2) Evaluation of Winding Properties

The negative electrode, separator, positive electrode, and separatorobtained in Section (20-1) were laminated in this order and rolled byapplying a winding tension of 250 gf several rounds like a spiral toprepare an electrode laminate. Ten electrode laminates were fabricated,visually observed with respect to the presence or absence of twist andwrinkle in the separators and evaluated in accordance with the followingevaluation criteria.

(Evaluation Criteria)

◯: No appearance defect such as twist and wrinkle was observed.

Δ: A single appearance defect such as twist and wrinkle was observed.

x: At least two appearance defects such as twist and wrinkle wereobserved.

(20-3) Evaluation of Cycle Characteristics of Battery <Assembly ofBattery>

The negative electrode, separator, positive electrode, and separatorobtained in Section (20-1) were laminated in this order and rolled byapplying a winding tension of 250 gf at a rolling rate of 45 mm/second,several rounds like a spiral to form an electrode laminate. Theelectrode laminate was housed in a stainless steel container having anouter diameter of 18 mm and a height of 65 mm. An aluminum tab guidedout from a positive electrode collector was weld to a terminal of thecover of the container; whereas, a nickel tab guided out from a negativeelectrode collector was welded to the wall of the container. Thereafter,the container was dried under vacuum at 80° C. for 12 hours. Theaforementioned non-aqueous electrolyte was injected in the batterycontainer assembled in an argon box and the battery container wassealed.

<Pretreatment>

The battery assembled was subjected to constant-current charging at acurrent value of ⅓C up to a voltage of 4.2 V and then subjected toconstant-voltage charging at a voltage of 4.2 V for 8 hours. Thereafter,the battery was discharged at a current value of ⅓C up to terminationvoltage of 3.0 V. Subsequently, the battery was subjected toconstant-current charging at a current value of 1C to a voltage of 4.2 Vand then subjected to constant-voltage charging at 4.2 V for 3 hours.Thereafter, the battery was discharged at a current value of 1C up totermination voltage of 3.0 V. Finally, the battery was subjected toconstant-current charging at a current value of 1C to 4.2 V and thensubjected to constant-voltage charging at 4.2 V for 3 hours. This wasspecified as a pretreatment. Note that 1C represents a current value atwhich the reference capacity of a battery is discharged for one hour.

<Cycle Test>

The battery pretreated was discharged under the following conditions:temperature of 25° C., a discharge current of 1 A, up to a dischargetermination voltage of 3 V, and thereafter charged at a charge currentof 1 A up to charge termination voltage of 4.2 V. This was specified asa single cycle. The cycle of charge-discharge was repeated and thecapacity retention rate after 200 cycles based on the initial capacitywas obtained. Based on the capacity retention rate, cyclecharacteristics were evaluated in accordance with the followingcriteria.

(Evaluation Criteria)

⊚: capacity retention rate of 95% or more and 100% or less

∘: capacity retention rate of 90% or more and less than 95%

x: capacity retention rate of less than 90%

Example A Production Example 1-1A (Production of Polyolefin MicroporousFilm 1A)

A high-density polyethylene (homopolymer) having Mv of 700,000 (45 partsby mass), a high-density polyethylene (homopolymer) having Mv of 300,000(45 parts by mass) and a mixture of a polypropylene (homopolymer) havingMv of 400,000 and a polypropylene (homopolymer) having Mv of 150,000 (ina mass ratio=4:3) (10 parts by mass) were dry-blended by a tumblerblender. To the obtained polyolefin mixture (99 parts by mass),tetrakis-[methylene-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane(1 part by mass) serving as an antioxidant was added and dry-blended byusing the tumbler blender again to obtain a mixture. The obtainedmixture was supplied to a double screw extruder through a feeder under anitrogen atmosphere. Furthermore, liquid paraffin (a kinetic viscosityof 7.59×10⁻⁵ m²/s at 37.78° C.) was injected into the extruder cylinderby a plunger pump. The driving conditions of the feeder and pump werecontrolled such that the ratio of liquid paraffin in the total mixtureto be extruded was 65 parts by mass, in other words, such that a polymerconcentration was 35 parts by mass.

Subsequently, they were melt-kneaded in the double screw extruder whilebeing heated at 230° C. and the obtained melt-kneaded product wasextruded on a cooling roller controlled at a surface temperature of 80°C., via a T-die. The extruded product was allowed to be in contact withthe cooling roller, molded (casted) and cooled to solidify to obtain asheet-like molded product. The sheet was stretched by a simultaneousbiaxial stretching machine at a stretching ratio of 7×6.4 times at atemperature of 112° C. and soaked in dichloromethane. After liquidparaffin was removed by extraction, the sheet was dried and stretchedtwofold by a tenter stretching machine at a temperature of 130° C. inthe transverse direction. Thereafter, the stretched sheet was relaxed inthe width direction by about 10% and subjected to a heat treatment toobtain polyolefin microporous film 1A shown in Table 1.

Physical properties of polyolefin microporous film 1A obtained weremeasured by the above methods. Furthermore, the obtained polyolefinmicroporous film was directly used as a separator and evaluated by theabove methods. The obtained results are shown in Table 1.

Production Example 1-2A (Production of Polyolefin Microporous Film 2A)

The same operation as in Production Example 1-1A was repeated exceptthat the stretching temperature and the relaxation rate were controlledto obtain polyolefin microporous film 2A. The obtained polyolefinmicroporous film 2A was evaluated by the above methods in the samemanner as in Production Example 1-1A. The obtained results are shown inTable 1.

Production Example 1-3A (Production of Polyolefin Microporous Film 3A)

A high-density polyethylene (homopolymer) having a viscosity averagemolecular weight of 700,000 (47.5 parts by mass), a high-densitypolyethylene (homopolymer) having a viscosity average molecular weightof 250,000 (47.5 parts by mass) and a polypropylene (homopolymer) havinga viscosity average molecular weight of 400,000 (5 parts by mass) weredry-blended by a tumbler blender. To the obtained polymer mixture (99parts by mass),pentaerythrityl-tetrakis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate](1 part by mass) serving as an antioxidant was added and dry-blended byusing the tumbler blender again to obtain a mixture of the polymers. Theobtained polymer mixture was replaced with nitrogen and then supplied toa double screw extruder through a feeder under a nitrogen atmosphere.Furthermore, liquid paraffin was injected into the extruder cylinder bya plunger pump.

They were melt-kneaded, and the feeder and pump were controlled suchthat the ratio of liquid paraffin in the total mixture to be extrudedwas 67 mass % (resin composition concentration: 33 mass %). Themelt-kneaded product was extruded on a cooling roller via a T-die andcasted to obtain a sheet-like molded product. Thereafter, the sameoperation was repeated as in Production Example 1-1A except that thestretching temperature and the relaxation rate were controlled to obtainpolyolefin microporous film 3A. Polyolefin microporous film 3A obtainedwas evaluated by the above methods in the same manner as in ProductionExample 1-1A. The obtained results are shown in Table 1.

Production Example 1-4A (Production of Polyolefin Microporous Film 4A)

An ultrahigh molecular weight polyethylene having a viscosity averagemolecular weight of 2,000,000 (25 parts by mass), a high-densitypolyethylene (homopolymer) having a viscosity average molecular weightof 700,000 (15 parts by mass), a high-density polyethylene having aviscosity average molecular weight of 250,000 (30 parts by mass) and apolyethylene copolymer (30 parts by mass) having a viscosity averagemolecular weight of 120,000 and a unit content of propylene of 1 mol %were dry-blended by a tumbler blender. To the obtained polymer mixture(99 parts by mass),pentaerythrityl-tetrakis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate](0.3 parts by mass) serving as an antioxidant was added and dry-blendedby using the tumbler blender again to obtain a mixture of the polymers.The obtained polymer mixture was replaced with nitrogen and thensupplied to a double screw extruder through a feeder under a nitrogenatmosphere. Furthermore, liquid paraffin was injected into the extrudercylinder by a plunger pump.

They were melt-kneaded, and the feeder and pump were controlled suchthat the ratio of liquid paraffin in the total mixture to be extrudedwas 65 mass % (resin composition concentration: 35 mass %). Themelt-kneaded product was extruded on a cooling roller via a T-die andcasted to obtain a sheet-like molded product. Thereafter, the sameoperation was repeated as in Production Example 1-1A except that thestretching temperature and the relaxation rate were controlled to obtainpolyolefin microporous film 4A. Polyolefin microporous film 4A obtainedwas evaluated by the above methods in the same manner as in ProductionExample 1-1A. The obtained results are shown in Table 1.

Production Example 1-5A (Production of Polyolefin Microporous Film 5A)

The same operation was repeated as in Production Example 1-3A exceptthat the stretching temperature and the relaxation rate were controlledto obtain polyolefin microporous film 5. Polyolefin microporous film 5obtained was evaluated by the above methods in the same manner as inProduction Example 1-1A. The obtained results are shown in Table 1.

Production Example 1-6A (Production of Polyolefin Microporous Film 6A)

An ultrahigh molecular weight polyethylene having a viscosity averagemolecular weight of 1,000,000 (19.2 parts by mass), a high-densitypolyethylene having a viscosity average molecular weight of 250,000(12.8 parts by mass), dioctyl phthalate (DOP) (48 parts by mass) andfine powder silica (20 parts by mass) were mixed, granulated andthereafter melt-kneaded by a double screw extruder provided with a T-dieat the front edge, extruded, extended from both sides by a heated rollerto obtain a sheet-like molded product having a thickness of 110 μm. DOPand fine powder silica were removed by extraction from the moldedproduct to prepare a microporous film. Two sheets of the microporousfilms were laminated, stretched 5 times in the MD at 120° C. and twofoldin the TD at 120° C. and finally treated with heat at 137° C. Theobtained polyolefin microporous film 6A was evaluated by the abovemethods in the same manner as in Production Example 1-1A. The obtainedresults are shown in Table 1.

Production Example 1-7A (Production of Polyolefin Microporous Film 7A)

Aluminum hydroxide oxide (an average particle size: 1.0 μm) (96.0 partsby mass) and acryl latex (solid substance concentration: 40%, an averageparticle size: 145 nm, the lowest film formation temperature: 0° C. orless) (4.0 parts by mass) and an aqueous ammonium polycarboxylatesolution (SN dispersant 5468, manufactured by San Nopco Limited) (1.0part by mass) were uniformly dispersed in water (100 parts by mass) toprepare a coating liquid. The coating liquid was applied to a surface ofpolyolefin resin porous film 1A by use of a microgravure coater anddried at 60° C. to remove water to obtain a porous layer having athickness of 2 μm. In this manner, polyolefin microporous film 7A wasobtained. Polyolefin microporous film 7A obtained was evaluated by theabove methods in the same manner as in Production Example 1-1A. Theobtained results are shown in Table 1.

Production Example 1-8A (Production of Polyolefin Microporous Film 8A)

A porous layer of 4 μm in thickness was formed on one of the surfaces ofpolyolefin microporous film 1A in the same manner as in ProductionExample 1-7A to obtain polyolefin microporous film 8A. Polyolefinmicroporous film 8A obtained was evaluated by the above methods in thesame manner as in Production Example 1-1A. The obtained results areshown in Table 1.

Production Example 1-9A (Production of Polyolefin Microporous Film 9A)

A porous layer of 3 μm in thickness was formed on one of the surfaces ofpolyolefin microporous film 2A in the same manner as in ProductionExample 1-7A to obtain polyolefin microporous film 9A. Polyolefinmicroporous film 9A obtained was evaluated by the above methods in thesame manner as in Production Example 1-1A. The obtained results areshown in Table 1.

Production Example 1-10A (Production of Polyolefin Microporous Film 10A)

A porous layer of 7 μm in thickness was formed on one of the surfaces ofpolyolefin microporous film 5A in the same manner as in ProductionExample 1-7A to obtain polyolefin microporous film 10A. Polyolefinmicroporous film 10A obtained was evaluated by the above methods in thesame manner as in Production Example 1-1A. The obtained results areshown in Table 1.

Production Example 1-11A (Production of Polyolefin Microporous Film 11A)

Fired kaolin (obtained by subjecting baking at high temperature to wetkaolin containing kaolinite (Al₂Si₂O₅(OH)₄) as a main component; anaverage particle size: 1.8 μm) (95.0 parts by mass), acryl latex (solidsubstance concentration: 40%, an average particle size: 220 nm, thelowest film formation temperature: 0° C. or less) (5.0 parts by mass)and an aqueous ammonium polycarboxylate solution (SN dispersant 5468,manufactured by San Nopco Limited) (0.5 parts by mass) were uniformlydispersed in water (180 parts by mass) to prepare a coating liquid. Thecoating liquid was applied to a surface of polyolefin microporous film3A by use of a microgravure coater, dried at 60° C. to remove water toobtain a porous layer having a thickness of 6 μm. In this manner,polyolefin microporous film 11A was obtained. Polyolefin microporousfilm 11A obtained was evaluated by the above methods in the same manneras in Production Example 1-1A. The obtained results are shown in Table1.

Production Example 1-12A (Production of Polyolefin Microporous Film 12A)

The same operation as in Production Example 1-1A was repeated exceptthat the stretching temperature and the relaxation rate were controlledto obtain a polyolefin microporous film having a weight per unit area:4.6 g/m², film thickness: 7 μm, porosity: 38%, air permeability: 150seconds, puncture strength: 270 g, average pore diameter: 0.070 μm. Aporous layer of 3 μm in thickness was formed on one of the surfaces ofthe polyolefin microporous film in the same manner as in ProductionExample 1-7A to obtain polyolefin microporous film 12A. Polyolefinmicroporous film 12A obtained was evaluated by the above methods in thesame manner as in Production Example 1-1A. The obtained results areshown in Table 1.

TABLE 1 Polyolefin microporous film No. 1A 2A 3A 4A 5A 6A 7A 8A Weightper unit area 7.0 5.3 6.4 10.0 6.4 8.4 Aluminum Aluminum (g/m²)hydroxide hydroxide oxide Film thickness (μm) 12 9 15 16 18 18 oxide (2μm) (4 μm) was Porosity (%) 40 40 59 38 62 51 was applied to applied toa Air permeability (s/100 cc) 150 150 75 380 89 90 a polyolefinpolyolefin Puncture strength (g) 320 300 440 510 440 400 microporousmicroporous film Average pore diameter 0.075 0.066 0.056 0.055 0.0510.110 film 1A 1A (μm) Thickness of inorganic — — — — — — 2 4 fillerlayer (μm) Stickiness 25° C. ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ 40° C. ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚Adhesiveness X X X X X X X X Winding properties ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ Cyclecharacteristics ◯ ⊚ ⊚ ◯ ⊚ ◯ ◯ ◯ Polyolefin microporous film No. 9A 10A11A 12A Weight per unit area Aluminum Aluminum Fired kaolin) Aluminumhydroxide oxide (3 μm) (g/m²) hydroxide oxide hydroxide oxide (6 μm waswas applied to a polyolefin Film thickness (μm) (3 μm) was (7 μm) wasapplied to a microporous film (weight per unit Porosity (%) applied to aapplied to a polyolefin area: 4.6 g/m², film thickness: 7 μm, Airpermeability (s/100 cc) polyolefin polyolefin microporous porosity: 38%,air Puncture strength (g) microporous film microporous film film 3Apermeability: 150 seconds, Average pore diameter 2A 5A puncturestrength: 270 g, (μm) average pore diameter: 0.070 μm) Thickness ofinorganic 3 7 6 3 filler layer (μm) Stickiness 25° C. ⊚ ⊚ ⊚ ⊚ 40° C. ⊚ ⊚⊚ ⊚ Adhesiveness X X X X Winding properties ⊚ ⊚ ⊚ ⊚ Cyclecharacteristics ⊚ ⊚ ⊚ ⊚

Production Example 2-1A (Production of Starting Polymer 1)

In a reaction container equipped with a stirrer, a reflux condenser, adriptank and a thermometer, ion exchange water (70.4 parts by mass),“Aqualon KH1025” (registered trade mark, a 25% aqueous solution,manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) (0.5 parts by mass) and“Adekaria soap SR1025” (registered trade mark, a 25% aqueous solution,manufactured by ADEKA CORP.) (0.5 parts by mass) were supplied. Theinterior temperature of the reaction container was raised to 80° C.While maintaining the temperature at 80° C., ammonium persulfate (anaqueous 2% solution) (7.5 parts by mass) was added.

Five minutes after the aqueous ammonium persulfate solution was added, amixture of methyl methacrylate (38.5 parts by mass), n-butyl acrylate(19.6 parts by mass), 2-ethylhexyl acrylate (31.9 parts by mass),methacrylate (0.1 part by mass), acrylic acid (0.1 part by mass),2-hydroxyethyl methacrylate (2 parts by mass), acrylamide (5 parts bymass), glycidyl methacrylate (2.8 parts by mass), trimethylolpropanetriacrylate (A-TMPT, manufactured by Shin-Nakamura Chemical Co., Ltd.)(0.7 parts by mass), “Aqualon KH1025” (registered trade mark, a 25%aqueous solution, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) (3parts by mass), “Adekaria soap SR1025” (registered trade mark, a 25%aqueous solution, manufactured by ADEKA CORP.) (3 parts by mass), sodiump-styrenesulfonate (0.05 parts by mass), ammonium persulfate (a 2%aqueous solution) (7.5 parts by mass),γ-methacryloxypropyltrimethoxysilane (0.3 parts by mass) and ionexchange water (52 parts by mass) was mixed by a homo mixer for 5minutes to prepare an emulsion. The obtained emulsion was added dropwisefrom the driptank to the reaction container over 150 minutes.

After completion of dropwise addition of the emulsion, the interiortemperature of the reaction container was maintained at 80° C. for 90minutes and thereafter reduced to room temperature. The obtainedemulsion was adjusted to pH=9.0 with an aqueous ammonium hydroxidesolution (an aqueous 25% solution) to obtain an acrylic copolymer latexof a concentration 40% (starting polymer 1A). Starting polymer 1Aobtained was evaluated by above methods. The obtained results are shownin Table 2.

Production Examples 2-2A to 2-8A (Starting Polymers 2A to 8A)

Acrylic copolymer latexes (starting polymers 2A to 8A) were obtained inthe same manner as in obtaining polymer 1A except that compositions ofmonomers and the other starting materials were changed as described inTable 2. Starting polymers 2A to 8A obtained were evaluated by the abovemethods. The obtained results are shown in Table 2.

Starting polymers 9A to 18A described below were evaluated by the abovemethods. The obtained results are shown in Table 2. Note that Tg valuesof starting polymers 9A to 18A were all rough estimations by the FOXformula.

Starting polymer 9A: styrene-butadiene polymer (particle size: 300 nm,Tg: 0° C., toluene-insoluble matter: 95%, degree of swelling with anelectrolyte solvent: 1.7 times)

Starting polymer 10A: styrene-butadiene polymer (particle size: 377 nm,Tg: 30° C., toluene-insoluble matter: 96%, degree of swelling with anelectrolyte solvent: 1.7 times)

Starting polymer 11A: styrene-butadiene polymer (particle size: 380 nm,Tg: 90° C., toluene-insoluble matter: 95%, degree of swelling with anelectrolyte solvent: 1.6 times)

Starting polymer 12A: acrylic polymer (particle size: 380 nm, Tg: 90°C., toluene-insoluble matter: 98%, degree of swelling with anelectrolyte solvent: 2.8 times), obtained by using the same monomers andstarting materials as used for obtaining starting polymers 1 to 8.

Starting polymer 13A: acrylic polymer (particle size: 50 nm, Tg: 90° C.,toluene-insoluble matter: 97%, degree of swelling with an electrolytesolvent: 2.9 times), obtained by using the same monomers and startingmaterials as used for obtaining starting polymers 1 to 8

Starting polymer 14A: acrylic polymer (particle size: 50 nm, Tg: 30° C.,toluene-insoluble matter: 99%, degree of swelling with an electrolytesolvent: 3.0 times), obtained by using the same monomers and startingmaterials as used for obtaining starting polymers 1 to 8

Starting polymer 15A: acrylic polymer (particle size: 500 nm, Tg: 30°C., toluene-insoluble matter: 98%, degree of swelling with anelectrolyte solvent: 2.7 times), obtained by using the same monomers andstarting materials as used for obtaining starting polymers 1 to 8

Starting polymer 16A: acrylic polymer (particle size: 500 nm, Tg: 90°C., toluene-insoluble matter: 96%, degree of swelling with anelectrolyte solvent: 3.2 times), obtained by using the same monomers andstarting materials as used for obtaining starting polymers 1 to 8

Starting polymer 17A: acrylic polymer (particle size: 1000 nm, Tg: 90°C., toluene-insoluble matter: 96%, degree of swelling with anelectrolyte solvent: 3.0 times), obtained by using the same monomers andstarting materials as used for obtaining starting polymers 1 to 8

Starting polymer 18A: acryl (core-shell) (particle size: 350 nm, coreTg: −20° C., shell Tg: 50° C., toluene-insoluble matter: 96%, degree ofswelling with an electrolyte solvent: 3.2 times) obtained by using thesame monomers and starting materials as used for obtaining startingpolymers 1 to 8.

TABLE 2 Starting polymer Active Low Tg High Tg Content Type Name ofstarting material ingredient 1A 2A 3A 4A 5A 6A 7A 8A Initial EmulsifyingKH1025 25% 0.5 1.8 1.8 0.34 0.5 0.34 0.34 0.32 supply agent SR1025 25%0.5 1.8 1.8 0.34 0.5 0.34 0.34 0.32 Ion exchange water — 70.4 70.4 70.470.4 70.4 70.4 70.4 70.4 Initiator APS (aq) 2% 7.5 7.5 7.5 7.5 7.5 7.57.5 7.5 Emulsion Monomer MMA 100% 38.5 30.5 41.3 15.9 52.5 71.5 89 55.5BA 100% 19.6 60.8 50 74.5 19.5 18.9 1.4 34.9 EHA 100% 31.9 2 2 2 20.4 22 2 Functional MAA 100% 0.1 1 1 0.1 0.1 0.1 0.1 0.1 group AA 100% 0.11.5 1.5 0.1 0.1 0.1 0.1 0.1 containing HEMA 100% 2 2 2 2 2 2 2 2 monomerAM 100% 5 0.2 0.2 5 5 5 5 5 GMA 100% 2.8 2 2 0.4 0.4 0.4 0.4 0.4Emulsifying KH1025 25% 3 3 3 3 3 3 3 2.6 agent SR1025 25% 3 3 3 3 3 3 32.6 NaSS 100% 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 CrosslinkingA-TMPT 100% 0.7 0.7 0.7 0.4 0.4 0.4 0.4 0.4 agent γ- 100% 0.3 0.3 0.30.3 0.3 0.3 0.3 0.3 methacryloxypropyltrimethoxysilane Initiator APS(aq) 2% 7.5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 Ion exchange water — 52 52 52 5252 52 52 52 Physical Glass-transition temperature Tg (° C.) −6 −15 0 −3015 55 95 25 property Particle size (50% particle size) (nm) 132 60 60140 138 144 161 140 of latex Toluene insoluble matter (%) 96% 95% 95%96% 96% 96% 95% 96% Degree of swelling with electrolyte solution (times)2.50 2.60 2.55 2.60 2.60 2.40 2.10 2.50 *Note that Tg values of startingpolymers 1A to 8A described in Table 2 were all rough estimations by theFOX formula. (Note) Names of starting materials in Table 2 MMA: methylmethacrylate BA: n-butyl acrylate EHA: 2-ethylhexyl acrylate MAA:methacrylate AA: acrylic acid HEMA: 2-hydroxyethyl methacrylate AM:acrylamide GMA: glycidyl methacrylate NaSS: sodium p-styrenesulfonateA-TMPT: trimethylolpropane triacrylate (manufactured by Shin-NakamuraChemical Co., Ltd.) KH1025: Aqualon KH1025 (registered trade mark,manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) SR1025: Adekaria soapSR1025 (registered trade mark, manufactured by ADEKA CORP.) APS:ammonium persulfate

Example 1A

Starting polymer 8A described in Table 2 (2.4 parts by mass on a solidbasis) and starting polymer 1A (0.6 parts by mass on a solid basis) wereweighed and dispersed in water (92.5 parts by mass) to prepare athermoplastic polymer-containing coating liquid. Subsequently, thecoating liquid was applied by use of a spray on one of the surfaces ofpolyolefin microporous film 1 described in Table 1, dried at 60° C. toremove water of the coating liquid. Similarly, the coating liquid wasapplied to the other surface and dried again to obtain a separator foran electricity storage device having a thermoplastic polymer on bothsurfaces of the polyolefin microporous film. The obtained separator wasevaluated by the above methods. The obtained results are shown in Table3.

Examples 2A to 40A, Comparative Examples 1A to 4A

Separators for an electricity storage device each were fabricated in thesame manner as in Example 1A except that a coating liquid containingthermoplastic polymers in combination as shown in Tables 3 to 6 wasapplied to both surfaces of a polyolefin microporous film by any one ofmethods (spray, gravure). The physical properties and evaluation resultsof the obtained separators are shown in Tables 3 to 6. Note that Tgvalues of the thermoplastic polymers shown in Tables 3 to 6 were valuesmeasured by the method described in Section (8) in the above.

TABLE 3 Example Example Example Example Example Example Example 1A 2A 3A4A 5A 6A 7A Polyolefin microporous film 1A 1A 1A 1A 1A 1A 1AThermoplastic Composition Starting polymer 8A 8A 6A 6A 6A 7A 7Apolymer-containing No. coating liquid Mixing ratio % 80 50 50 80 80 5080 Starting polymer 1A 1A 2A 2A 3A 2A 2A No. Mixing ratio % 20 50 50 2020 50 20 Concentration of % 3 3 3 3 3 3 3 thermoplastic polymer Coatingmethod Spray Spray Spray Spray Spray Spray Spray Existence form ofthermoplastic polymer (coated form) Dots Dots Dots Dots Dots Dots DotsAverage particle size of particulate thermoplastic 0.15 0.15 0.15 0.150.15 0.15 0.15 polymer (μm) Glass-transition temperature ofthermoplastic ° C. 35 35 64 64 64 105 105 polymer 5 5 −5 −5 10 −5 −5Area ratio of polyolefin microporous film % 30 30 30 30 30 30 30 coveredwith thermoplastic polymer coating layer Area ratio of particulatethermoplastic polymer % 90 50 50 90 90 50 90 Coating thickness μm 0.30.3 0.3 0.3 0.3 0.3 0.3 Wettability ◯ ◯ ◯ ◯ ◯ ◯ ◯ Adhesiveness tosubstrate ◯ ◯ ◯ ◯ ◯ ◯ ◯ Stickiness Peel 25° C. ⊚ ◯ ⊚ ⊚ ⊚ ⊚ ⊚ strength40° C. ◯ Δ ⊚ ⊚ ⊚ ⊚ ⊚ Heat-peel strength 80° C. ◯ ◯ ◯ ◯ ◯ ◯ ◯Adhesiveness (relative to electrode) ◯ ◯ ◯ ◯ ◯ ◯ ◯ Winding properties ◯◯ ◯ ◯ ◯ ◯ ◯ Cycle characteristics ◯ ◯ ⊚ ⊚ ⊚ ⊚ ⊚ Example Example ExampleExample Example Example Example 8A 9A 10A 11A 12A 13A 14A Polyolefinmicroporous film 1A 1A 1A 1A 1A 1A 1A Thermoplastic Composition Startingpolymer 6A 6A 8A 6A 6A 10A  11A  polymer-containing No. coating liquidMixing ratio % 80 80 20 80 80 80 80 Starting polymer 3A 3A 2A 3A 4A 9A9A No. Mixing ratio % 20 20 80 20 20 20 20 Concentration of % 3 10 3 303 30 30 thermoplastic polymer Coating method Spray Spray Spray SpraySpray Gravure Gravure Existence form of thermoplastic polymer (coatedform) Dots Dots Dots Dots Dots Dots Dots Average particle size ofparticulate thermoplastic 0.15 0.15 0.15 0.15 0.15 0.35 0.35 polymer(μm) Glass-transition temperature of thermoplastic ° C. 64 64 35 64 6440 100 polymer 10 10 −5 10 −20 10 10 Area ratio of polyolefinmicroporous film % 40 15 30 5 30 30 30 covered with thermoplasticpolymer coating layer Area ratio of particulate thermoplastic polymer %90 90 20 90 90 90 90 Coating thickness μm 0.5 1.0 0.3 2.5 0.3 1.0 1.0Wettability ◯ ◯ ◯ ◯ ◯ ◯ ◯ Adhesiveness to substrate ◯ ◯ ◯ ◯ ◯ ◯ ◯Stickiness Peel 25° C. ⊚ ⊚ Δ ◯ ⊚ ◯ ⊚ strength 40° C. ⊚ ⊚ X Δ ◯ Δ ⊚Heat-peel strength 80° C. ◯ ◯ ◯ ◯ ◯ ◯ ◯ Adhesiveness (relative toelectrode) ◯ Δ Δ X ◯ ◯ ◯ Winding properties ◯ ◯ Δ ◯ ◯ ◯ ◯ Cyclecharacteristics ⊚ ◯ ◯ ◯ ⊚ ◯ ◯

TABLE 4 Example Example Example Example Example Example Example 15A 16A17A 18A 19A 20A 21A Polyolefin microporous film 1A 1A 1A 1A 1A 1A 1AThermoplastic Composition Starting polymer 11A  12A  12A  12A  12A  13A 14A  polymer-containing No. coating liquid Mixing ratio % 80 80 80 80 8080 80 Starting polymer 1A 1A 1A 1A 1A 1A 1A No. Mixing ratio % 20 20 2020 20 20 20 Concentration of % 30 30 30 30 3 30 30 thermoplastic polymerCoating method Gravure Gravure Gravure Gravure Spray Gravure GravureExistence form of thermoplastic polymer (coated form) Dots Dots DotsDots Dots Dots Dots Average particle size of particulate thermoplastic0.35 0.38 0.38 0.38 0.38 0.05 0.05 polymer (μm) Glass-transitiontemperature of thermoplastic ° C. 100 100 100 100 100 100 40 polymer 5 55 5 5 5 5 Area ratio of polyolefin microporous film % 30 30 10 50 30 3030 covered with thermoplastic polymer coating layer Area ratio ofparticulate thermoplastic polymer % 90 90 90 90 90 90 90 Coatingthickness μm 1.0 1.0 1.0 1.0 0.5 1.0 1.0 Wettability ◯ ◯ ◯ ◯ ◯ ◯ ◯Adhesiveness to substrate ◯ ◯ ◯ ◯ ◯ ◯ ◯ Stickiness Peel 25° C. ⊚ ⊚ ⊚ ⊚ ⊚⊚ ◯ strength 40° C. ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ◯ Heat-peel strength 80° C. ◯ ◯ ◯ ◯ ◯ ◯◯ Adhesiveness (relative to electrode) ◯ ◯ Δ ◯ ◯ ◯ ◯ Winding properties◯ ◯ ◯ ◯ ◯ ◯ ◯ Cycle characteristics ◯ ◯ ⊚ ◯ ◯ ◯ ◯ Example ExampleExample Example Example Example Example 22A 23A 24A 25A 26A 27A 28APolyolefin microporous film 1A 1A 1A 1A 1A 1A 1A ThermoplasticComposition Starting polymer 6A 6A 12A  15A  16A  17A  18A polymer-containing No. coating liquid Mixing ratio % 80 80 90 90 90 9080 Starting polymer 1A 1A 1A 1A 1A 1A 1A No. Mixing ratio % 20 20 10 1010 10 20 Concentration of % 30 30 30 30 30 30 30 thermoplastic polymerCoating method Gravure Gravure Gravure Gravure Gravure Gravure GravureExistence form of thermoplastic polymer (coated form) Dots grid DotsDots Dots Dots Dots Average particle size of particulate thermoplastic0.15 0.15 0.38 0.5 0.5 1 0.35 polymer (μm) Glass-transition temperatureof thermoplastic ° C. 64 64 100 40 100 100 50 polymer 5 5 5 5 5 5 5 −20Area ratio of polyolefin microporous film % 30 50 30 30 30 30 30 coveredwith thermoplastic polymer coating layer Area ratio of particulatethermoplastic polymer % 90 90 90 90 90 90 90 Coating thickness μm 1.02.0 1.0 1.0 1.0 2.0 1.0 Wettability ◯ ◯ ◯ ◯ ◯ ◯ ◯ Adhesiveness tosubstrate ◯ ◯ ◯ ◯ ◯ ◯ ◯ Stickiness Peel 25° C. ⊚ ⊚ ⊚ ◯ ⊚ ⊚ ⊚ strength40° C. ⊚ ⊚ ⊚ ◯ ⊚ ⊚ ◯ Heat-peel strength 80° C. ◯ ◯ ◯ X X X ◯Adhesiveness (relative to electrode) ◯ ◯ ◯ Δ Δ Δ ◯ Winding properties ◯◯ ◯ ◯ ◯ ◯ ◯ Cycle characteristics ◯ ◯ ◯ ◯ ◯ ◯ ◯

TABLE 5 Example Example Example Example Example Example 29A 30A 31A 32A33A 34A Polyolefin microporous film 2A 3A 4A 5A 6A 7A ThermoplasticComposition Starting polymer No. 6A 6A 6A 6A 6A 6A polymer-containingMixing ratio % 80 80 80 80 80 80 coating liquid Starting polymer No. 1A1A 1A 1A 1A 1A Mixing ratio % 20 20 20 20 20 20 Concentration of % 30 3030 30 30 30 thermoplastic polymer Coating method Gravure Gravure GravureGravure Gravure Gravure Existence form of thermoplastic polymer (coatedform) Dots Dots Dots Dots Dots Dots Average particle size of particulatethermoplastic polymer 0.15 0.15 0.15 0.15 0.15 0.15 (μm)Glass-transition temperature of thermoplastic ° C. 64 64 64 64 64 64polymer 5 5 5 5 5 5 Area ratio of polyolefin microporous film covered %30 30 30 30 30 30 with thermoplastic polymer coating layer Area ratio ofparticulate thermoplastic polymer % 90 90 90 90 90 90 Coating thicknessμm 2.0 2.0 2.0 2.0 2.0 2.0 Wettability ◯ ◯ ◯ ◯ ◯ ◯ Adhesiveness tosubstrate ◯ ◯ ◯ ◯ ◯ ◯ Stickiness Peel strength 25° C. ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ 40° C.⊚ ⊚ ⊚ ⊚ ⊚ ⊚ Heat-peel strength 80° C. ◯ ◯ ◯ ◯ ◯ ◯ Adhesiveness (relativeto electrode) ◯ ◯ ◯ ◯ ◯ ◯ Winding properties ◯ ◯ ◯ ◯ ◯ ◯ Cyclecharacteristics ⊚ ⊚ ◯ ⊚ ◯ ◯ Example Example Example Example ExampleExample 35A 36A 37A 38A 39A 40A Polyolefin microporous film 7A 8A 9A 10A11A 12A Thermoplastic Composition Starting polymer No. 6A 6A 6A 6A 6A 6Apolymer-containing Mixing ratio % 80 80 80 80 80 80 coating liquidStarting polymer No. 1A 1A 1A 1A 1A 1A Mixing ratio % 20 20 20 20 20 20Concentration of % 5 30 30 30 30 30 thermoplastic polymer Coating methodSpray Gravure Gravure Gravure Gravure Gravure Existence form ofthermoplastic polymer (coated form) Dots Dots Dots Dots Dots DotsAverage particle size of particulate thermoplastic polymer 0.15 0.150.15 0.15 0.15 0.15 (μm) Glass-transition temperature of thermoplastic °C. 64 64 64 64 64 64 polymer 5 5 5 5 5 5 Area ratio of polyolefinmicroporous film covered % 30 30 30 30 30 30 with thermoplastic polymercoating layer Area ratio of particulate thermoplastic polymer % 90 90 9090 90 90 Coating thickness μm 0.5 2.0 2.0 2.0 2.0 1.0 Wettability ◯ ◯ ◯◯ ◯ ◯ Adhesiveness to substrate ◯ ◯ ◯ ◯ ◯ ◯ Stickiness Peel strength 25°C. ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ 40° C. ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ Heat-peel strength 80° C. ◯ ◯ ◯ ◯ ◯ ◯Adhesiveness (relative to electrode) ◯ ◯ ◯ ◯ ◯ ◯ Winding properties ◯ ◯◯ ◯ ◯ ◯ Cycle characteristics ◯ ◯ ⊚ ⊚ ⊚ ⊚

TABLE 6 Comparative Comparative Comparative Comparative Example 1AExample 2A Example 3A Example 4A Polyolefin microporous film 1A 1A 1A 1AThermoplastic polymer- Composition Starting polymer No. 6A 1A 5A 6Acontaining coating liquid Mixing ratio % 100 100 100 80 Starting polymerNo. — — — 1A Mixing ratio % 0 0 0 20 Concentration of % 3 3 3 30thermoplastic polymer Coating method Spray Spray Spray Gravure Existenceform of thermoplastic polymer (coated form) Dots Dots Dots wholly coatedAverage particle size of particulate thermoplastic polymer (μm) 0.15 — —0.15 Glass-transition temperature of thermoplastic polymer ° C. 64 5 2664 — — — 5 Area ratio of polyolefin microporous film covered % 30 30 30100 with thermoplastic polymer coating layer Area ratio of particulatethermoplastic polymer % 100 0 0 90 Coating thickness μm — 0.3 0.3 1.0Wettability X ◯ ◯ ◯ Adhesiveness to substrate X ◯ ◯ ◯ Stickiness Peelstrength 25° C. — X ◯ ⊚ 40° C. — X X ⊚ Heat-peel strength 80° C. — ◯ ◯ ◯Adhesiveness (relative to electrode) — Δ ◯ ⊚ Winding properties — X ◯ ◯Cycle characteristics — ◯ ◯ X

Note that in the separator for the electricity storage device describedeach in Examples A, the resin constituting a thermoplastic polymercoating layer has glass-transition temperatures in the ranges of 20° C.or more and less than 20° C. and a feature in that the peel strength wassmall in the press conditions at 25° C. and large in press conditions at80° C. From this, it was presumed that, in the thermoplastic polymercoating layer, a large amount of thermoplastic resin having aglass-transition temperature of 20° C. or more was present on the sideof the outermost surface of a separator for an electricity storagedevice; whereas a large amount of thermoplastic resin having aglass-transition temperature of less than 20° C. was present on the sideof the interface between a polyolefin microporous film and athermoplastic polymer coating layer.

Example B Production Example 1-1B

High-density polyethylene 1 (14.25 parts by mass) having a viscosityaverage molecular weight of 250,000 and a melting point of 137° C.,high-density polyethylene 2 (14.25 parts by mass) having a viscosityaverage molecular weight of 700,000 and a melting point of 137° C., apolypropylene (1.5 parts by mass) having a viscosity average molecularweight of 400,000 and a melting point of 163° C. andtetrakis-[methylene-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane(0.2 parts by mass) serving as an antioxidant were blended to prepare astarting material.

Individual compositions each were loaded via a feeder of a double screwextruder having an aperture of 25 mm L/D=48. Furthermore, liquidparaffin (68 parts by mass) was injected by a side feed to eachextruder. The composition was kneaded in the conditions of 200° C. and200 rpm while controlling such that an extrusion amount per hour was 16kg, and thereafter extruded from the T-die at 200° C. Immediately afterthe extrusion, the extruded material was cooled to solidify by a castroll conditioned at 40° C. and molded into a sheet having a desiredthickness. The sheet was stretched by a simultaneous biaxial stretchingmachine at a stretching ratio of 7×6.4 times at a temperature of 112° C.and soaked in methylene chloride. Then, liquid paraffin was removed byextraction, and thereafter dried and stretched by a tenter stretchingmachine in the transverse direction. Thereafter, the stretched sheet wasrelaxed in the width direction and subjected to a heat treatment toobtain polyolefin microporous film 1B. The physical properties of theobtained microporous film are shown in Table 7.

Production Examples 1-2B to 1-8B

Polyolefin microporous films 2B to 8B each were obtained by changing therelaxation rate of the stretched sheet in the width direction in thesame manner as in Production Example 1-1B. The physical properties ofthe obtained microporous films are shown in Table 7.

Production Examples 2-9B to 2-13B

Polyolefin microporous films 9B to 13B were obtained in the same manneras in Production Examples 1-7A to 1-11A. The physical properties of theobtained microporous films are shown in Table 7.

TABLE 7 Polyolefin microporous film 1B 2B 3B 4B 5B 6B 7B 8B 9B 10BRelaxation rate in width 24 14 13 23 13 11 11 10 Boehmite (2 μm) wasBoehmite (4 μm) was direction (%) applied to a polyolefin applied to apolyolefin Weight per unit area (g/m²) 7.4 5.3 7.0 8.5 9.4 6.4 6.4 8.4microporous film 1B microporous film 1B Film thickness (μm) 12 9 12 1416 15 18 18 Coating-layer thickness (μm) — — — — — — — — Porosity (%) 3637 40 36 39 59 62 51 Air permeability (s/100 cc) 230 159 150 292 168 7589 90 Puncture strength (g) 400 310 320 501 386 440 440 400 Handlingperformance ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Adhesiveness to electrode active X X X XX X X X X X material Rate characteristics 99 99.5 99 99 99 99.5 99.5 9999 99 Polyolefin microporous film 11B 12B 13B Relaxation rate in widthdirection Boehmite (3 μm) Boehmite (7 μm) was Fired kaolin (6 μm) (%)was applied to a applied to a polyolefin was applied to a Weight perunit area (g/m²) polyolefin microporous film 5B polyolefin microporousFilm thickness (μm) microporous film 5B film 3B Coating-layer thickness(μm) Porosity (%) Air permeability (s/100 cc) Puncture strength (g)Handling performance ◯ ◯ ◯ Adhesiveness to electrode active X X Xmaterial Rate characteristics 99 99.5 99

Production Example 2-1B (Production of Acrylic Emulsion Coating Liquid

In a reaction container equipped with a stirrer, a reflux condenser, adriptank and a thermometer, ion exchange water (70.4 parts), “AqualonKH1025” (registered trade mark, a 25% aqueous solution, manufactured byDaiichi Kogyo Seiyaku Co., Ltd.) (0.5 parts) and “Adekaria soap SR1025”(registered trade mark, a 25% aqueous solution, manufactured by ADEKACORP.) (0.5 parts) were supplied. The interior temperature of thereaction container was raised to 80° C. While maintaining thetemperature at 80° C., ammonium persulfate (an aqueous 2% solution) (7.5parts) was added.

Five minutes after the aqueous ammonium persulfate (APS) solution wasadded, an emulsion, which was prepared by mixing a mixture of methylmethacrylate (MMA) (38.9 parts), n-butyl acrylate (BA) (26.5 parts),2-ethylhexyl acrylate (EHA) (27 parts), methacrylic acid (MAA) (0.1part), acrylic acid (AA) (0.1 part), 2-hydroxyethyl methacrylate (HEMA)(2 parts), acrylamide (AM) (5 parts), glycidyl methacrylate (GMA) (0.4parts), trimethylolpropane triacrylate (A-TMPT, manufactured byShin-Nakamura Chemical Co., Ltd.) (2 parts), “Aqualon KH1025”(registered trade mark, a 25% aqueous solution, manufactured by DaiichiKogyo Seiyaku Co., Ltd.) (3 parts), “Adekaria soap SR1025” (registeredtrade mark, a 25% aqueous solution, manufactured by ADEKA CORP.) (3parts), sodium p-styrenesulfonate (NaSS) (0.05 parts), ammoniumpersulfate (a 2% aqueous solution) (7.5 parts),γ-methacryloxypropyltrimethoxysilane (0.3 parts) and ion exchange water(52 parts), by a homo mixer for 5 minutes, was added dropwise from adriptank to the reaction container over 150 minutes.

After completion of dropwise addition of the emulsion, the interiortemperature of the reaction container was maintained at 80° C. for 90minutes and thereafter reduced to room temperature. The obtainedemulsion was adjusted to pH=9.0 with an aqueous ammonium hydroxidesolution (an aqueous 25% solution) to obtain thermoplasticpolymer-containing coating liquid 1B.

Production Examples 2-2B to 2-10B

Thermoplastic polymer-containing coating liquids 2B to 10B were obtainedin the same manner as in Production Example 1-1B except thatcompositions of monomers and the other starting materials used werechanged as shown in Table 8.

TABLE 8 Active Coating liquid Content Type Name of starting materialingredient 1B 2B 3B 4B 5B Initial Emulsifying KH1025 25% 0.5 0.5 0.5 0.50.5 supply agent SR1025 25% 0.5 0.5 0.5 0.5 0.5 Ion exchange water —70.4 70.4 70.4 70.4 70.4 Initiator APS (aq) 2% 7.5 7.5 7.5 7.5 7.5Emulsion Monomer MMA 100% 38.9 38.9 6.34 63.4 44.9 BA 100% 26.5 26.5 1414 19.5 EHA 100% 27 27 15 15 20 Functional MAA 100% 0.1 0.1 0.1 0.1 0.1group AA 100% 0.1 0.1 0.1 0.1 0.1 containing HEMA 100% 2 2 2 2 10monomer AM 100% 5 5 5 5 5 GMA 100% 0.4 0.4 0.4 0.4 0.4 EmulsifyingKH1025 25% 3 3 3 3 3 agent SR1025 25% 3 3 3 3 3 NaSS 100% 0.05 0.05 0.050.05 0.05 Crosslinking A-TMPT 100% 2 0.4 2 0.4 0.4 agent γ- 100% 0.3 0.30.3 0.3 0.3 methacryloxypropyltrimethoxysilane Initiator APS (aq) 2% 7.57.5 7.5 7.5 7.5 Ion exchange water — 52 52 52 52 52 PhysicalGlass-transition temperature Tg (° C.) −6 −6 35 35 15 property Particlesize (50% particle size) (nm) 142 141 135 135 139 of latex Tolueneinsoluble matter (%) 97 95 97 96 96 Degree of swelling with electrolytesolution (times) 1.5 3.8 1.6 3.0 3.4 Active Coating liquid Content TypeName of starting material ingredient 6B 7B 8B 9B 10B Initial EmulsifyingKH1025 25% 0.5 0.5 0.5 0.5 0.5 supply agent SR1025 25% 0.5 0.5 0.5 0.50.5 Ion exchange water — 70.4 70.4 70.4 70.4 70.4 Initiator APS (aq) 2%7.5 7.5 7.5 7.5 7.5 Emulsion Monomer MMA 100% 55.4 46.4 32.9 77.4 38.9BA 100% 18 22.5 29.5 7 26.5 EHA 100% 19 23.5 30 8 27 Functional MAA 100%0.1 0.1 0.1 0.1 0.1 group AA 100% 0.1 0.1 0.1 0.1 0.1 containing HEMA100% 2 2 2 2 2 monomer AM 100% 5 5 5 5 5 GMA 100% 0.4 0.4 0.4 0.4 0.4Emulsifying KH1025 25% 3 3 3 3 3 agent SR1025 25% 3 3 3 3 3 NaSS 100%0.05 0.05 0.05 0.05 0.05 Crosslinking A-TMPT 100% 0.4 4 4 0.4 0.1 agentγ- 100% 0.3 0.3 0.3 0.3 0.1 methacryloxypropyltrimethoxysilane InitiatorAPS (aq) 2% 7.5 7.5 7.5 7.5 7.5 Ion exchange water — 52 52 52 52 52Physical Glass-transition temperature Tg (° C.) 20 5 −15 55 −6 propertyParticle size (50% particle size) (nm) 139 140 148 131 142 of latexToluene insoluble matter (%) 96 99 99 96 88 Degree of swelling withelectrolyte solution (times) 3.6 0.9 1.0 3.3 5.5 *Note that Tg values ofthermoplastic polymers described in Table 8 were all rough estimationsby the FOX formula. (Note) Names of starting materials in Table 8 MMA:methyl methacrylate BA: n-butyl acrylate EHA: 2-ethylhexyl acrylate MAA:methacrylate AA: acrylic acid HEMA: 2-hydroxyethyl methacrylate AM:acrylamide GMA: glycidyl methacrylate NaSS: sodium p-styrenesulfonateA-TMPT: trimethylolpropane triacrylate (manufactured by Shin-NakamuraChemical Co., Ltd.) KH1025: Aqualon KH1025 (registered trade mark,manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) SR1025: Adekaria soapSR1025 (registered trade mark, manufactured by ADEKA CORP.) APS:ammonium persulfate

Example 1B

Thermoplastic polymer-containing coating liquid 1B (7.5 parts by mass)was uniformly dispersed in water (92.5 parts by mass) to prepare acoating liquid. The coating liquid was applied to a surface ofpolyolefin microporous film 1B by use of a gravure coater and dried at60° C. to remove water. Furthermore, the coating liquid was appliedsimilarly to the other surface and dried to obtain a porous film (aseparator for an electricity storage device). The physical propertiesand evaluation results of the obtained porous film are shown in Table 9.

Examples 2B to 8B

Porous films (separators for an electricity storage device) wereprepared in the same manner as in Example 1A except that thermoplasticpolymer-containing coating liquids 2B to 5B were used. The physicalproperties and evaluation results of the thermoplasticpolymer-containing coating liquids used, polyolefin microporous filmsand the obtained porous films (separators for an electricity storagedevice) are shown in Table 9.

Example 9B

To polyolefin microporous film 1B, thermoplastic polymer-containingcoating liquid 5B was applied by a spray and dried at 60° C. to removewater. Furthermore, thermoplastic polymer-containing coating liquid 5Bwas applied similarly to the other surface and dried to obtain a porousfilm (a separator for an electricity storage device). The physicalproperties and evaluation results of the obtained porous film (aseparator for an electricity storage device) are shown in Table 9.

Example 10B

To polyolefin microporous film 1B, thermoplastic polymer-containingcoating liquid 5B was applied by inkjet so as to obtain a resolution of180 Dpi and dried at 60° C. to remove water. Furthermore, thermoplasticpolymer-containing coating liquid 5B was applied similarly to the othersurface and dried to obtain a porous film (a separator for anelectricity storage device). The physical properties and evaluationresults of the obtained porous film (a separator for an electricitystorage device) are shown in Table 9.

Examples 11B to 13B

To polyolefin microporous film 1B, thermoplastic polymer-containingcoating liquid 5B was applied by a gravure coater, which was processedto form dots, and dried at 60° C. to remove water. Furthermore,thermoplastic polymer-containing coating liquid 5B was applied similarlyto the other surface and dried to obtain a porous film (a separator foran electricity storage device). The physical properties and evaluationresults of the obtained porous films (separators for an electricitystorage device) are shown in Table 9.

Examples 14B to 27B

Porous films (separators for an electricity storage device) wereprepared in the same manner as in Example 9B except that polyolefinmicroporous films and thermoplastic polymer-containing coating liquidsdescribed in Tables 9 and 10 were used. The physical properties andevaluation results of the obtained porous films (separators for anelectricity storage device) are shown in Tables 9 and 10.

Comparative Examples 1B to 3B

Porous films (separators for an electricity storage device) wereprepared in the same manner as in Example 1B except that polyolefinmicroporous films and thermoplastic polymer-containing coating liquidsdescribed in Table 11 were used. The physical properties and evaluationresults of the obtained porous films (separators for an electricitystorage device) are shown in Table 11.

[Rate Characteristics] (Fabrication of Electrode)

a. Fabrication of Positive Electrode

Lithium cobalt composite oxide (LiCoO₂) (92.2 mass %) as a positiveelectrode active material, scale-like graphite and acetylene black (2.3mass % for each) as a conductive material and polyvinylidene fluoride(PVDF) (3.2 mass %) as a binder were dispersed in N-methyl pyrrolidone(NMP) to prepare a slurry. The slurry was applied to one of the surfacesof an aluminum foil of 20 μm in thickness serving as a positiveelectrode collector by a die coater, dried at 130° C. for 3 minutes andthereafter subjected to compression molding by a roll pressing machine.The application herein was controlled such that the active materialcoating amount of positive electrode was 250 g/m² and the bulk densityof the active material was 3.00 g/cm³.

b. Fabrication of Negative Electrode

Artificial graphite (96.9 mass %) as a negative electrode activematerial, an ammonium salt of carboxymethylcellulose (1.4 mass %) and astyrene-butadiene copolymer latex (1.7 mass %) as a binder weredispersed in purified water to prepare a slurry. The slurry was appliedto one of the surfaces of a copper foil of 12 μm in thickness serving asa negative electrode collector by a die coater, dried at 120° C. for 3minutes and thereafter subjected to compression molding by a rollpressing machine. The application herein was controlled such that thecoating amount of negative electrode active material was 106 g/m² andthe bulk density of the active material was 1.35 g/cm³.

(Fabrication of Battery)

a. Fabrication of Positive Electrode

The positive electrode fabricated in the same manner as in Section(Fabrication of electrode) a., was punched to obtain a circularelectrode having an area of 2.00 cm².

b. Fabrication of Negative Electrode

The negative electrode fabricated in the same manner as in Section(Fabrication of electrode) b., was punched to obtain a circularelectrode having an area of 2.05 cm².

c. Non-Aqueous Electrolyte

In a solvent mixture of ethylene carbonate:ethylmethyl carbonate=1:2(volume ratio), LiPF6 as a solute was dissolved so as to have aconcentration 1.0 ml/L to prepare a non-aqueous electrolyte.

d. Assemble of Battery

The porous film of Example 1B was used as a separator. A negativeelectrode, the porous film and a positive electrode were laminated inthis order from the bottom such that the active material surface of thepositive electrode faced to the active material surface of the negativeelectrode. The laminate was housed in a stainless steel metal containerprovided with a cover, which was insulated from a container main body,such that the copper foil of the negative electrode and the aluminumfoil of the positive electrode were in contact with the container mainbody and the cover, respectively. Into the container, a non-aqueouselectrolyte was injected and the container was sealed airtight to obtaina non-aqueous electrolyte secondary battery (Example 1B).

The simple battery assembled was charged at 25° C. at a current value of3 mA (about 0.5 C) up to a battery voltage of 4.2 V and then the currentvalue was allowed to decrease from 3 mA while maintaining a voltage at4.2 V. In this manner, after the battery was fabricated, the initialcharge of the battery and the following discharge at a current value of3 mA up to a battery voltage of 3.0 V were performed in total for about6 hours.

Subsequently, the battery was charged up to a battery voltage of 4.2 Vat 25° C. at a current value of 6 mA (about 1.0 C) and then the currentvalue was allowed to decrease from 6 mA while maintaining a voltage at4.2 V. In this manner, the charge of the battery and the followingdischarge at a current value of 6 mA up to a battery voltage of 3.0 Vwere performed in total for about 3 hours. The discharge capacity atthis time was specified as 1C discharge capacity (mAh).

Subsequently, at 25° C., the battery was charged at a current value of 6mA (about 1.0 C) up to a battery voltage of 4.2 V and the current valuewas allowed to decrease from 6 mA while maintaining a voltage at 4.2 V.In this manner, the charge of the battery and the following discharge ata current value of 12 mA (about 2.0 C) up to a battery voltage of 3.0 Vwere performed in total for about 3 hours. The discharge capacity atthis time was specified as 2C discharge capacity (mAh).

The rate of 2C discharge capacity to 1C discharge capacity wascalculated and the value was specified as rate characteristics. Theevaluation results are shown in Table 9.

Rate characteristics (%)=(2C discharge capacity/1C dischargecapacity)×100

Examples 2B to 27B and Comparative Examples 1B to 3B (Battery)

Batteries (Examples 2B to 27B and Comparative Examples 1B to 3B) werefabricated in the same manner as in Example 1B except that porous filmsof Examples 2B to 27B and Comparative Examples 1B to 3B were used as theseparators in place of the porous film of Example 1B. The ratecharacteristics of the obtained batteries were evaluated. The evaluationresults are shown in Tables 9 to 11.

TABLE 9 Example No. Example Example Example Example Example ExampleExample 1B 2B 3B 4B 5B 6B 7B Thermoplastic Adhesive resin 1B 2B 3B 4B 1B1B 5B polymer Glass-transition temperature −6 −6 35 35 −6 −6 15 (° C.)Degree of swelling (times) 1.5 3.8 1.6 3 1.5 1.5 3.4 Content of adhesiveresin 0.1 0.1 0.1 0.1 1.3 0.05 0.2 (g/m²) Surface coating ratio (%) 6060 60 60 75 60 5 Existence form of adhesive Non-dots Non-dots Non-dotsNon-dots Non-dots Non-dots Non-dots resin Average major axis (μm) — — —— — — — Thickness (μm) 0.3 0.2 0.3 0.2 0.2 0.2 0.1 Porous filmPolyolefin microporous 1B 1B 1B 1B 1B 1B 1B film Film thickness (μm)12.3 12.2 12.3 12.2 12.2 12.2 12.1 Air permeability (s/100 cc) 430 420440 420 520 330 300 Adhesiveness between ◯ ◯ ◯ ◯ ◯ ◯ ◯ thermoplasticpolymer and polyolefin microporous film Handling performance Δ Δ ◯ ◯ Δ Δ◯ Adhesiveness to electrode ◯ ◯ ◯ ◯ ◯ X X active material Battery Ratecharacteristics 43.1 38.1 45.1 39.4 30.2 44.3 58.7 Example No. ExampleExample Example Example Example Example Example 8B 9B 10B 11B 12B 13B14B Thermoplastic Adhesive resin 5B 5B 5B 5B 5B 5B 5B polymerGlass-transition temperature 15 15 15 15 15 15 15 (° C.) Degree ofswelling (times) 3.4 3.4 3.4 3.4 3.4 3.4 3.4 Content of adhesive resin0.2 0.2 0.2 0.2 0.2 0.2 0.2 (g/m²) Surface coating ratio (%) 60 30 30 3030 30 30 Existence form of adhesive Non-dots Dots Dots Dots Dots DotsDots resin Average major axis (μm) — 50 30 100 500 1000 50 Thickness(μm) 0.1 0.5 0.5 0.5 0.5 0.5 0.3 Porous film Polyolefin microporous 1B1B 1B 1B 1B 1B 2B film Film thickness (μm) 12.1 12.5 12.5 12.5 12.5 12.59.3 Air permeability (s/100 cc) 400 300 300 300 300 300 220 Adhesivenessbetween ◯ ◯ ◯ ◯ ◯ ◯ ◯ thermoplastic polymer and polyolefin microporousfilm Handling performance ◯ ◯ ◯ ◯ ◯ ◯ ◯ Adhesiveness to electrode ◯ ◯ ◯◯ ◯ ◯ ◯ active material Battery Rate characteristics 40.2 53.5 53 52 5353 74.2

TABLE 10 Example No. Example Example Example Example Example ExampleExample 15B 16B 17B 18B 19B 20B 21B Thermoplastic Adhesive resin 5B 6B7B 5B 5B 5B 5B polymer Glass-transition temperature (° C.) 15 20 5 15 1515 15 Degree of swelling (times) 3.4 3.6 0.9 3.4 3.4 3.4 3.4 Content ofadhesive resin (g/m²) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Surface coating ratio(%) 30 30 30 30 30 30 30 Existence form of adhesive resin Dots Dots DotsDots Dots Dots Dots Average major axis (μm) 50 50 50 50 50 50 50Thickness (μm) 0.5 0.5 0.5 0.5 0.5 3.3 0.3 Porous film Polyolefinmicroporous film 3B 3B 3B 4B 5B 6B 7B Film thickness (μm) 12.5 12.5 12.514.5 16.5 18.3 18.3 Air permeability (s/100 cc) 200 200 200 355 220 150160 Adhesiveness between ◯ ◯ ◯ ◯ ◯ ◯ ◯ thermoplastic polymer andpolyolefin microporous film Handling performance ◯ ◯ Δ ◯ ◯ ◯ ◯Adhesiveness to electrode active ◯ ◯ ◯ ◯ ◯ ◯ ◯ material Battery Ratecharacteristics 69.4 65.6 70.6 37.3 43.1 70.1 72.3 Example No. ExampleExample Example Example Example Example 22B 23B 24B 25B 26B 27BThermoplastic Adhesive resin 5B 5B 5B 5B 5B 5B polymer Glass-transitiontemperature (° C.) 15 15 15 15 15 15 Degree of swelling (times) 3.4 3.43.4 3.4 3.4 3.4 Content of adhesive resin (g/m²) 0.2 0.2 0.2 0.2 0.2 0.2Surface coating ratio (%) 30 30 30 30 30 30 Existence form of adhesiveresin Dots Dots Dots Dots Dots Dots Average major axis (μm) 50 50 50 5050 50 Thickness (μm) 0.3 0.2 0.3 0.2 2.2 3.2 Porous film Polyolefinmicroporous film 8B 9B 10B  11B  12B  13B  Film thickness (μm) 18.3 14.216.3 12.2 25.2 21.2 Air permeability (s/100 cc) 160 180 180 190 140 120Adhesiveness between ◯ ◯ ◯ ◯ ◯ ◯ thermoplastic polymer and polyolefinmicroporous film Handling performance ◯ ◯ ◯ ◯ ◯ ◯ Adhesiveness toelectrode active ◯ ◯ ◯ ◯ ◯ ◯ material Battery Rate characteristics 58.655.1 58.1 57.7 75.1 55.4

TABLE 11 Comparative Example Comparative Comparative Comparative Example1B Example 2B Example 3B Thermoplastic Adhesive resin 8B 9B 10B polymerGlass-transition temperature (° C.) −15 55 −6 Degree of swelling (times)1.5 3.8 5.5 Content of adhesive resin (g/m²) 0.1 0.1 0.1 Surface coatingratio (%) 60 60 60 Existence form of adhesive resin Non-dots Non-dotsNon-dots Average major axis (μm) — — — Thickness (μm) 0.2 0 0.3 Porousfilm Polyolefin microporous film 1B 1B 1B Film thickness (μm) 12.2 —12.3 Air permeability (s/100 cc) 450 — 460 Adhesiveness betweenthermoplastic polymer and ◯ X ◯ polyolefin microporous film Handlingperformance X — Δ Adhesiveness to electrode active material ◯ — ◯Battery Rate characteristics 45.3 — 24.1

This application is based on the Japanese Patent Application No.2012-166179 filed Jul. 26, 2012 with Japan Patent Office and JapanesePatent Application No. 2012-234852 filed Oct. 24, 2012 with Japan PatentOffice, the contents of which are incorporated herein by reference.

INDUSTRIAL APPLICABILITY

According to the present invention, it is possible to provide aseparator excellent in adhesiveness to electrodes as well as excellentin handling performance.

Accordingly, the present invention is useful as a separator forelectricity storage devices including batteries such as non-aqueouselectrolyte secondary batteries, condensers and capacitors.

1.-10. (canceled)
 11. A porous film having a polyolefin microporous filmand a thermoplastic polymer coating layer covering at least a part of atleast one of surfaces of the polyolefin microporous film, wherein thethermoplastic polymer coating layer contains a thermoplastic polymerhaving a glass-transition temperature in a range of −10° C. or more and40° C. or less, and a degree of swelling of the thermoplastic polymerwith an electrolytic solution of 5 times or less.
 12. The porous filmaccording to claim 11, wherein the thermoplastic polymer coating layerhas an average thickness of 1.5 μm or less.
 13. The porous filmaccording to claim 11, wherein an area ratio of the polyolefinmicroporous film covered with the thermoplastic polymer coating layer is70% or less based on 100% of a total area of the polyolefin microporousfilm.
 14. The porous film according to claim 11, wherein thethermoplastic polymer has a gel fraction of 90% or more.
 15. The porousfilm according to claim 11, wherein the thermoplastic polymer coatinglayer, on the polyolefin microporous film, has a portion containing thethermoplastic polymer and a portion not containing the thermoplasticpolymer in a sea-island configuration, and the portion containing thethermoplastic polymer is formed in a dot pattern.
 16. The porous filmaccording to claim 15, wherein the dot has an average major axis of 20to 1000 μm.